Acid dyes, process for the production thereof and their use

ABSTRACT

Dyes of formula (1) 
                         
their preparation and use are described.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. §371)of PCT/EP2014/072635, filed Oct. 22, 2014, which claims benefit ofEuropean Application No. 13190670.3, filed Oct. 29, 2013, both of whichare incorporated herein by reference in their entirety.

The present invention relates to the technical field of dyestuffs fordyeing and printing of hydroxyl- and/or carboxamido-containing material.

Acid dyes with pyridine couplers are known from prior art and can beused as colorants in different applications, see for example U.S. Pat.Nos. 3,959,250 A, 5,468,848 A, EP 2 457 956 A and WO 2007/045825 A.

However, in the context of the dyeing and printing of hydroxyl- and/orcarboxamido-containing material the known dyes have a number oftechnical disadvantages, which require improvement.

One such disadvantage is, that many of them are comprising heavy metalssuch as Cu, Cr or Ni. Such heavy metals are critical from atoxicological as well as an environmental point of view and shall thusbe excluded.

Surprisingly, it has now been found that the dyes of formula (1) asdescribed below show highly advantageous properties over the known dyes.These include high tinctorial strength with high brilliancy as well ashigh fastness properties such as wash, contact and light fastness on thematerials mentioned above, on blends containing them as well as onmicrofibres. Most importantly, dyes of formula (1) are substantiallyheavy metal free and provide dyeings that are levelled. Metals may onlybe present as counter ions and are selected from the groups of alkaliand earth alkali metals, which do not have such effects as heavy metals.

If heavy metals are present at all in the dyes of the present inventionthey do not result from being integral part of the dye but are coursedby the production process in general. Reasons in general for theseimpurities can be impurities resulting from educts and catalysts beingused in the respective reactions—the levels of such impurities can bemanaged and be kept well below those recommended e.g. by ETAD® and wouldthus be below 100 ppm for Cr, below 250 ppm for Cu and below 200 ppm forNi just to mention the values for the metals mentioned above. This is asignificant improvement as compared to dyes where such metals arepresent at molar levels.

The present invention refers to dyes of formula (1) and mixtures thereof

wherein

R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independent of each other is hydrogen,alkyl, alkoxy, halogen, trifluoromethyl or SO₃M, whereby at least two ofthem are SO₃M,

R⁹, R¹⁰, R¹¹, R¹² independent of each other is hydrogen, alkyl,substituted alkyl, alkyl chain interrupted by one or two heteroatoms,alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl,heterocycloalkyl, cyano, acyloxy, alkylcarbonyl, acylamino,alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino,dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl,alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, alkylureido or SO₃M,

R¹³ and R¹⁸ independent of each other is cyano, carbamoyl, substitutedcarbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl orhalogen,

R¹⁴ and R¹⁹ independent of each other is hydrogen, alkyl, cycloalkyl,trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino,hydroxyl, monocycloalkyl-amino, monoalkyl-amino, di(cyclo)alkyl-amino,dialkyl-amino, monoaryl-amino, diaryl-amino,monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio,arylthio or

is alkyl substituted by one or more substituents selected from the groupconsisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl,aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM,alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino,arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido,alkylureido and phenylureido,

R¹⁵, R¹⁶, R¹⁷, R²⁰, R²¹ and R²² independent of each other is hydrogen,alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl,heterocycloalkyl, carbamoyl, alkylureido, phenylureido,hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl,alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, ami noalkyloxyalkyl,aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl,heteroarylalkyl, heterocycloalkylalkyl

or

alkyl interrupted by one or more heteroatoms selected from the groupconsisting of oxygen and sulfur

or

alkyl substituted by one or more substituents selected from the groupconsisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino,N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino,N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo-alkyl-amino,N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino,N,N-mono-aryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino,ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl,thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl,heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy,aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl,N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl,N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl,N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl,sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl,N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl,N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl,N-monoalkyl-N-monoarylsulfamoyl and SO₃M

or

alkyl interrupted by one or more heteroatoms selected from the groupconsisting of oxygen and sulfur and substituted by one or moresubstituents selected from the group consisting of hydroxy, aryl,cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino,N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino,N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino,N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino,N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido,halogen, cyano, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl,trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl,alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl,N-monocycloalkyl-carbamoyl, N-monoalkyl-carbamoyl,N,N-dicycloalkyl-carbamoyl, N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl,N,N-diaryl-carbamoyl, N-mono-cycloalkyl-N-monoarylcarbamoyl,N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl,N-monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl,N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl, N,N-diaryl-sulfamoyl,N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamoyland SO₃M,

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaliearth metal or a monovalent organic cation,

the dyes of formula (1) have two to six sulfonic acid groups

and

whereby the bonds with unfixed attachment points on the pyridinecouplers mean that the amino rests bearing the substituents R¹⁵ and R¹⁶,and —OR¹⁷, respectively can be positioned ortho or para to R¹³, meaningthat when the amino rest bearing the substituents R¹⁵ and R¹⁶ ispositioned ortho to R¹³, the —OR¹⁷ is positioned para to R¹³, and viceversa;

and

the same applies to the amino rests bearing the substituents R²⁰ andR²¹, and —OR²², respectively that can be positioned ortho or para toR¹⁸, meaning that when the amino rest bearing the substituents R²⁰ andR²¹ is positioned ortho to R¹⁸, the —OR²² is positioned para to R¹⁸, andvice versa.

This invention refers to all tautomeric and geometric isomers of thedyes of formula (1) and mixtures thereof.

Alkyl groups appearing in this invention may be straight-chain orbranched and are (C₁-C₁₂)-alkyl groups, preferably (C₁-C₈)-alkyl groups,for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert-butyl andmethylbutyl.

The same applies to alkoxy groups which accordingly are preferably(C₁-C₈)-alkoxy, for example methoxy and ethoxy, to thioalkoxy groups,which are preferably (C₁-C₈)-thioalkoxy, for example —SCH₃ or —SC₂H₅.

Cycloalkyl groups are preferably (C₃-C₈)-cycloalkyl and preferablycyclopentyl and cyclohexyl. The term cyloalkyl comprises for the purposeof the present invention substituted cycloalkyl groups and unsaturatedcycloalkyl groups as well. A preferred group of this type iscyclopentenyl. Preferred substituents are alkyl, hydroxyalkyl, halogen,hydroxyl, alkoxy, acyl, cyano, nitro, amino, monoalkylamino,dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino,monoalkyl-mono(hydroxy-alkyl)amino, carbamoyl, sulfamoyl, acylamino,ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Alkenyl groups may be straight-chain or branched and are preferably(C₂-C₆)-groups for example vinyl and allyl. The term alkenyl comprisesfor the purpose of the present invention alkynyl groups as well, forexample ethynyl and propargyl.

Aryl groups appearing in this invention are preferably phenyl ornaphthyl. The terms phenyl and naphthyl comprise unsubstituted as wellas substituted phenyl and naphthyl. Preferred substituents are alkyl,cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy,alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino,mono(hydroxyalkyl)amino, bis(hydroxyalkyl)amino,monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino,ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Heteroaryl groups are preferably pyridine, pyrimidine, pyridazine,pyrazine, pyrrole, imidazole, pyrazole, 1,2,4-thiadiazole,1,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole,benzothiazole, benzoisothiazole, 1,3,4-thiadiazole, furane, oxazole,benz-oxazole and isoxazole. The term heteroaryl comprises the abovegroups in unsubstituted as well as in substituted form. Preferredsubstituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy,alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino,mono(hydroxyalkyl)amino, bis(hydroxyalkyl)amino,mono-alkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino,ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Heterocycloalkyl groups are preferably pyrrolidine, piperidine,morpholine, tetrahydrofuran or piperazine. The term heterocycloalkylcomprises the above groups in unsubstituted as well as in substitutedform. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl,alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino,dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino,mono-alkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino,aminocarbonyl-amino, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Halogen is preferably chlorine, bromine or fluorine.

M is preferably hydrogen, lithium, sodium, potassium or mono-, di-, tri-or tetra-(C₁-C₄)-alkylammonium.

Particular preferred embodiments of the present invention are the dyesof formula (1a) and mixtures thereof

wherein

R^(1a), R^(2a), R^(3a), R^(4a), R^(5a), R⁶, R^(7a) and R^(8a)independent of each other is hydrogen, alkyl, alkoxy, halogen,trifluoromethyl or SO₃M, whereby at least two of them are SO₃M,

R^(9a), R^(10a), R^(11a) and R^(12a) independent of each other ishydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, trifluoromethyl,(C₁-C₄)-acylamino or SO₃M,

R^(13a) and R^(18a) independent of each other is cyano, carbamoyl oralkoxycarbonyl,

R^(14a) and R^(19a) independent of each other is unsubstituted, linearor branched (C₁-C₄)-alkyl, unsubstituted (C₅-C₇)-cycloalkyl orsubstituted (C₅-C₇)-cycloalkyl with one or more substituents preferablyselected from the group consisting of methyl, ethyl, isobutyl,sec-butyl, tert-butyl and methylbutyl,

R^(15a), R^(16a) R^(17a), R^(20a), R^(21a) and R^(22a) independent ofeach other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl,cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido,phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl,amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl,aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl,aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl

or

alkyl interrupted by one or more heteroatoms selected from the groupconsisting of oxygen and sulfur

or

alkyl substituted by one or more substituents selected from the groupconsisting of hydroxy, aryl, cycloalkyl, alkoxy, amino,N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino,N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino,N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino,N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino,ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl,alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl,alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M

or

alkyl interrupted by one or more heteroatoms selected from the groupconsisting of oxygen and sulfur and substituted by one or moresubstituents selected from the group consisting of hydroxy, aryl,cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino,N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino,N-monocycloalkyl-amino, N,N-dicycloalkyl-amino,N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino,N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido,halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl,trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy,aryloyloxy, carbamoyl, sulfamoyl and SO₃M

and

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaliearth metal or a monovalent organic cation.

In especially preferred dyes of formula (1a)

R^(1a), R^(3a), R^(4a), R^(5a), R^(6a) and R^(8a) independent of eachother is SO₃M, hydrogen, alkyl, alkoxy or halogen, whereby at least twoof them are SO₃M,

R^(2a) and R^(7a) is hydrogen,

R^(9a), R^(10a), R^(11a) and R^(12a) independent of each other ishydrogen, methyl, methoxy, ethoxy, halogen, —SO₃M or acetylamino,

R^(13a) and R^(18a) independent of each other is cyano or carbamoyl,

R^(14a) and R^(19a) is methyl,

R^(15a), R^(16a), R^(20a) and R^(21a) independent of each other ishydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl,3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl,1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl,2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl,2-methoxyethyl, 3-methoxypropyl, 2-cyanoethyl, 2-(methylthio)ethyl,2-fluoroethyl, 2-chloroethyl, 3-chloropropyl,2-(2-hydroxyethylsulfanyl)-ethyl,2-(2-tertbutylsulfanylethanesulfonyl)methyl, 2-(2-hydroxyethoxy)propyl,2-(2-hydroxy ethoxy)ethyl, 3-(4-hydroxybutoxy)propyl,2-(2-hydroxyethanesulfonyl)-ethyl, 3-(2-phenoxy-ethoxy)-propyl,3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl

or

(C₂-C₆)-alkyl substituted by COOM or by SO₃M,

R^(17a) and R^(22a) independent from each other is hydrogen, (C₁-C₆)alkyl or (C₁-C₆) alkyl interrupted by —O— or —S—

and

M is hydrogen, sodium, potassium, lithium or ammonium.

Examples of preferred dyes of formula (1a) are the compounds of formulae(1a¹ to 1a⁴⁰⁴) and mixtures thereof (Table 1): hereby R^(1a) and R^(8a)are hydrogen

TABLE 1 S/No R^(3a) R^(4a) R^(5a) R^(6a) R^(10a)/R^(12a) R^(9a)/R^(11a)R^(13a)/R^(18a) R^(17a)/R^(22a) R^(15a)/R^(20a) R^(16a)/R^(21a) 1a¹ SO₃HH H SO₃H Methyl Methyl CN H Methyl H 1a² H SO₃H SO₃H H 1a³ SO₃H H H SO₃HMethyl Methyl CN H Ethyl H 1a⁴ H SO₃H SO₃H H 1a⁵ SO₃H H H SO₃H MethylMethyl CN H Propyl H 1a⁶ H SO₃H SO₃H H 1a⁷ SO₃H H H SO₃H Methyl MethylCN H Butyl H 1a⁸ H SO₃H SO₃H H 1a⁹ SO₃H H H SO₃H Methyl Methyl CN HPentyl H 1a¹⁰ H SO₃H SO₃H H 1a¹¹ SO₃H H H SO₃H Methyl Methyl CN H HexylH 1a¹² H SO₃H SO₃H H 1a¹³ SO₃H H H SO₃H Methyl Methyl CN H Cyclobutyl H1a¹⁴ H SO₃H SO₃H H 1a¹⁵ SO₃H H H SO₃H Methyl Methyl CN H Cyclopentyl H1a¹⁶ H SO₃H SO₃H H 1a¹⁷ SO₃H H H SO₃H Methyl Methyl CN H Cyclohexyl H1a¹⁸ H SO₃H SO₃H H 1a¹⁹ SO₃H H H SO₃H Methyl Methyl CN H 2-Methylcyclohexyl H 1a²⁰ H SO₃H SO₃H H 1a²¹ SO₃H H H SO₃H Methyl Methyl CN H3-Methyl cyclohexyl H 1a²² H SO₃H SO₃H H 1a²³ SO₃H H H SO₃H MethylMethyl CN H Isopropyl H 1a²⁴ H SO₃H SO₃H H 1a²⁵ SO₃H H H SO₃H MethylMethyl CN H Sec-butyl H 1a²⁶ H SO₃H SO₃H H 1a²⁷ SO₃H H H SO₃H MethylMethyl CN H 2-Methylbutyl H 1a²⁸ H SO₃H SO₃H H 1a²⁹ SO₃H H H SO₃H MethylMethyl CN H 1-Ethyl propyl H 1a³⁰ H SO₃H SO₃H H 1a³¹ SO₃H H H SO₃HMethyl Methyl CN H 1,2-Dimethyl propyl H 1a³² H SO₃H SO₃H H 1a³³ SO₃H HH SO₃H Methyl Methyl CN H Tert-butyl H 1a³⁴ H SO₃H SO₃H H 1a³⁵ SO₃H H HSO₃H Methyl Methyl CN H 3-Methyl butyl H 1a³⁶ H SO₃H SO₃H H 1a³⁷ SO₃H HH SO₃H Methyl Methyl CN H Pentan-2-yl H 1a³⁸ H SO₃H SO₃H H 1a³⁹ SO₃H H HSO₃H Methyl Methyl CN H 2-Ethylhexyl H 1a⁴⁰ H SO₃H SO₃H H 1a⁴¹ SO₃H H HSO₃H Methyl Methyl CN H 2,2-Dimethyl propyl H 1a⁴² H SO₃H SO₃H H 1a⁴³SO₃H H H SO₃H Methyl Methyl CN H Phenyl H 1a⁴⁴ H SO₃H SO₃H H 1a⁴⁵ SO₃H HH SO₃H Methyl Methyl CN H Benzyl H 1a⁴⁶ H SO₃H SO₃H H 1a⁴⁷ SO₃H H H SO₃HNHCOCH₃ OMe CN H Methyl H 1a⁴⁸ H SO₃H SO₃H H 1a⁴⁹ SO₃H H H SO₃H NHCOCH₃OMe CN H Ethyl H 1a⁵⁰ H SO₃H SO₃H H 1a⁵¹ SO₃H H H SO₃H NHCOCH₃ OMe CN HPropyl H 1a⁵² H SO₃H SO₃H H 1a⁵³ SO₃H H H SO₃H MHCOCH₃ OMe CN H Butyl H1a⁵⁴ H SO₃H SO₃H H 1a⁵⁵ SO₃H H H SO₃H NHCOCH₃ OMe CN H Pentyl H 1a⁵⁶ HSO₃H SO₃H H 1a⁵⁷ SO₃H H H SO₃H NHCOCH₃ OMe CN H Hexyl H 1a⁵⁸ H SO₃H SO₃HH 1a⁵⁹ SO₃H H H SO₃H NHCOCH₃ OMe CN H Cyclobutyl H 1a⁶⁰ H SO₃H SO₃H H1a⁶¹ SO₃H H H SO₃H NHCOCH₃ OMe CN H Cyclopentyl H 1a⁶² H SO₃H SO₃H H1a⁶³ SO₃H H H SO₃H NHCOCH₃ OMe CN H Cyclohexyl H 1a⁶⁴ H SO₃H SO₃H H 1a⁶⁵SO₃H H H SO₃H NHCOCH₃ OMe CN H 2-Methyl cyclohexyl H 1a⁶⁶ H SO₃H SO₃H H1a⁶⁷ SO₃H H H SO₃H NHCOCH₃ OMe CN H 3-Methyl cyclohexyl H 1a⁶⁸ H SO₃HSO₃H H 1a⁶⁹ SO₃H H H SO₃H NHCOCH₃ OMe CN H Isopropyl H 1a⁷⁰ H SO₃H SO₃HH 1a⁷¹ SO₃H H H SO₃H NHCOCH₃ OMe CN H Sec-butyl H 1a⁷² H SO₃H SO₃H H1a⁷³ SO₃H H H SO₃H NHCOCH₃ OMe CN H 2-Methyl butyl H 1a⁷⁴ H SO₃H SO₃H H1a⁷⁵ SO₃H H H SO₃H NHCOCH₃ OMe CN H 1-Ethyl propyl H 1a⁷⁶ H SO₃H SO₃H H1a⁷⁷ SO₃H H H SO₃H NHCOCH₃ OMe CN H 1,2-Dimethyl propyl H 1a⁷⁸ H SO₃HSO₃H H 1a⁷⁹ SO₃H H H SO₃H NHCOCH₃ OMe CN H Tert-butyl H 1a⁸⁰ H SO₃H SO₃HH 1a⁸¹ SO₃H H H SO₃H NHCOCH₃ OMe CN H 3-Methyl butyl H 1a⁸² H SO₃H SO₃HH 1a⁸³ SO₃H H H SO₃H NHCOCH₃ OMe CN H Pentan-2-yl H 1a⁸⁴ H SO₃H SO₃H H1a⁸⁵ SO₃H H H SO₃H NHCOCH₃ OMe CN H 2-Ethyl hexyl H 1a⁸⁶ H SO₃H SO₃H H1a⁸⁷ SO₃H H H SO₃H NHCOCH₃ OMe CN H 2,2-Dimethyl propyl H 1a⁸⁸ H SO₃HSO₃H H 1a⁸⁹ SO₃H H H SO₃H NHCOCH₃ OMe CN H Phenyl H 1a⁹⁰ H SO₃H SO₃H H1a⁹¹ SO₃H H H SO₃H NHCOCH₃ OMe CN H Benzyl H 1a⁹² H SO₃H SO₃H H 1a⁹³SO₃H H H SO₃H Methyl Methyl CONH₂ H Methyl H 1a⁹⁴ H SO₃H SO₃H H 1a⁹⁵SO₃H H H SO₃H Methyl Methyl CONH₂ H Ethyl H 1a⁹⁶ H SO₃H SO₃H H 1a⁹⁷ SO₃HH H SO₃H Methyl Methyl CONH₂ H Propyl H 1a⁹⁸ H SO₃H SO₃H H 1a⁹⁹ SO₃H H HSO₃H Methyl Methyl CONH₂ H Butyl H 1a¹⁰⁰ H SO₃H SO₃H H 1a¹⁰¹ SO₃H H HSO₃H Methyl Methyl CONH₂ H Pentyl H 1a¹⁰² H SO₃H SO₃H H 1a¹⁰³ SO₃H H HSO₃H Methyl Methyl CONH₂ H Hexyl H 1a¹⁰⁴ H SO₃H SO₃H H 1a¹⁰⁵ SO₃H H HSO₃H Methyl Methyl CONH₂ H Cyclobutyl H 1a¹⁰⁶ H SO₃H SO₃H H 1a¹⁰⁷ SO₃H HH SO₃H Methyl Methyl CONH₂ H Cyclopentyl H 1a¹⁰⁸ H SO₃H SO₃H H 1a¹⁰⁹SO₃H H H SO₃H Methyl Methyl CONH₂ H Cyclohexyl H 1a¹¹⁰ H SO₃H SO₃H H1a¹¹¹ SO₃H H H SO₃H Methyl Methyl CONH₂ H 2-Methyl cyclohexyl H 1a¹¹² HSO₃H SO₃H H 1a¹¹³ SO₃H H H SO₃H Methyl Methyl CONH₂ H 3-Methylcyclohexyl H 1a¹¹⁴ H SO₃H SO₃H H 1a¹¹⁵ SO₃H H H SO₃H Methyl Methyl CONH₂H Isopropyl H 1a¹¹⁶ H SO₃H SO₃H H 1a¹¹⁷ SO₃H H H SO₃H Methyl MethylCONH₂ H Sec-butyl H 1a¹¹⁸ H SO₃H SO₃H H 1a¹¹⁹ SO₃H H H SO₃H MethylMethyl CONH₂ H 2-Methyl butyl H 1a¹²⁰ H SO₃H SO₃H H 1a¹²¹ SO₃H H H SO₃HMethyl Methyl CONH₂ H 1-Ethyl propyl H 1a¹²² H SO₃H SO₃H H 1a¹²³ SO₃H HH SO₃H Methyl Methyl CONH₂ H 1,2-Dimethyl propyl H 1a¹²⁴ H SO₃H SO₃H H1a¹²⁵ SO₃H H H SO₃H Methyl Methyl CONH₂ H Tert-butyl H 1a¹²⁶ H SO₃H SO₃HH 1a¹²⁷ SO₃H H H SO₃H Methyl Methyl CONH₂ H 3-Methyl butyl H 1a¹²⁸ HSO₃H SO₃H H 1a¹²⁹ SO₃H H H SO₃H Methyl Methyl CONH₂ H Pentan-2-yl H1a¹³⁰ H SO₃H SO₃H H 1a¹³¹ SO₃H H H SO₃H Methyl Methyl CONH₂ H 2-Ethylhexyl H 1a¹³² H SO₃H SO₃H H 1a¹³³ SO₃H H H SO₃H Methyl Methyl CONH₂ H2,2-Dimethyl propyl H 1a¹³⁴ H SO₃H SO₃H H 1a¹³⁵ SO₃H H H SO₃H MethylMethyl CONH₂ H Phenyl H 1a¹³⁶ H SO₃H SO₃H H 1a¹³⁷ SO₃H H H SO₃H MethylMethyl CONH₂ H Benzyl H 1a¹³⁸ H SO₃H SO₃H H 1a¹³⁹ SO₃H H H SO₃H MethylMethyl CONH₂ H 3-(4-Hydroxybutoxy)- H 1a¹⁴⁰ H SO₃H SO₃H H propyl 1a¹⁴¹SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H Methyl H 1a¹⁴² H SO₃H SO₃H H 1a¹⁴³SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H Ethyl H 1a¹⁴⁴ H SO₃H SO₃H H 1a¹⁴⁵ SO₃HH H SO₃H MHCOCH₃ OMe CONH₂ H Propyl H 1a¹⁴⁶ H SO₃H SO₃H H 1a¹⁴⁷ SO₃H H HSO₃H NHCOCH₃ OMe CONH₂ H Butyl H 1a¹⁴⁸ H SO₃H SO₃H H 1a¹⁴⁹ SO₃H H H SO₃HNHCOCH₃ OMe CONH₂ H Pentyl H 1a¹⁵⁰ H SO₃H SO₃H H 1a¹⁵¹ SO₃H H H SO₃HNHCOCH₃ OMe CONH₂ H Hexyl H 1a¹⁵² H SO₃H SO₃H H 1a¹⁵³ SO₃H H H SO₃HNHCOCH₃ OMe CONH₂ H Cyclobutyl H 1a¹⁵⁴ H SO₃H SO₃H H 1a¹⁵⁵ SO₃H H H SO₃HNHCOCH₃ OMe CONH₂ H Cyclopentyl H 1a¹⁵⁶ H SO₃H SO₃H H 1a¹⁵⁷ SO₃H H HSO₃H NHCOCH₃ OMe CONH₂ H Cyclohexyl H 1a¹⁵⁸ H SO₃H SO₃H H 1a¹⁵⁹ SO₃H H HSO₃H NHCOCH₃ OMe CONH₂ H 2-Methyl cyclohexyl H 1a¹⁶⁰ H SO₃H SO₃H H 1a¹⁶¹SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H 3-Methyl cyclohexyl H 1a¹⁶² H SO₃HSO₃H H 1a¹⁶³ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H Isopropyl H 1a¹⁶⁴ H SO₃HSO₃H H 1a¹⁶⁵ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H Sec-butyl H 1a¹⁶⁶ H SO₃HSO₃H H 1a¹⁶⁷ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H 2-Methyl butyl H 1a¹⁶⁸ HSO₃H SO₃H H 1a¹⁶⁹ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H 1-Ethyl propyl H1a¹⁷⁰ H SO₃H SO₃H H 1a¹⁷¹ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H 1,2-Dimethylpropyl H 1a¹⁷² H SO₃H SO₃H H 1a¹⁷³ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ HTert-butyl H 1a¹⁷⁴ H SO₃H SO₃H H 1a¹⁷⁵ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H3-Methyl butyl H 1a¹⁷⁶ H SO₃H SO₃H H 1a¹⁷⁷ SO₃H H H SO₃H NHCOCH₃ OMeCONH₂ H Pentan-2-yl H 1a¹⁷⁸ H SO₃H SO₃H H 1a¹⁷⁹ SO₃H H H SO₃H NHCOCH₃OMe CONH₂ H 2-Ethyl hexyl H 1a¹⁸⁰ H SO₃H SO₃H H 1a¹⁸¹ SO₃H H H SO₃HNHCOCH₃ OMe CONH₂ H 2,2-Dimethyl propyl H 1a¹⁸² H SO₃H SO₃H H 1a¹⁸³ SO₃HH H SO₃H NHCOCH₃ OMe CONH₂ H Phenyl H 1a¹⁸⁴ H SO₃H SO₃H H 1a¹⁸⁵ SO₃H H HSO₃H NHCOCH₃ OMe CONH₂ H Benzyl H 1a¹⁸⁶ H SO₃H SO₃H H 1a¹⁸⁷ SO₃H H HSO₃H Methyl Methyl CN H Allyl H 1a¹⁸⁸ H SO₃H SO₃H H 1a¹⁸⁹ SO₃H H H SO₃HMethyl Methyl CN H 3-Methoxy propyl H 1a¹⁹⁰ H SO₃H SO₃H H 1a¹⁹¹ SO₃H H HSO₃H Methyl Methyl CN H 2-Hydroxy ethyl H 1a¹⁹² H SO₃H SO₃H H 1a¹⁹³ SO₃HH H SO₃H Methyl Methyl CN H 3-(4-Hydroxybutoxy)- H 1a¹⁹⁴ H SO₃H SO₃H Hpropyl 1a¹⁹⁵ SO₃H H H SO₃H Methyl Methyl CN H 2-(2-Hydroxy H 1a¹⁹⁶ HSO₃H SO₃H H ethoxy)ethyl 1a¹⁹⁷ SO₃H H H SO₃H Methyl Methyl CN H H H1a¹⁹⁸ H SO₃H SO₃H H 1a¹⁹⁹ SO₃H H H SO₃H Methyl Methyl CN H 3-Isopropoxypropyl H 1a²⁰⁰ H SO₃H SO₃H H 1a²⁰¹ SO₃H H H SO₃H Methyl Methyl CN H4-Ethoxy butyl H 1a²⁰² H SO₃H SO₃H H 1a²⁰³ SO₃H H H SO₃H NHCOCH₃ OMe CNH 2-Hydroxy ethyl H 1a²⁰⁴ H SO₃H SO₃H H 1a²⁰⁵ SO₃H H H SO₃H NHCOCH₃ OMeCN H 3-(4-Hydroxy H 1a²⁰⁶ H SO₃H SO₃H H butoxy)propyl 1a²⁰⁷ SO₃H H HSO₃H NHCOCH₃ OMe CN H H H 1a²⁰⁸ H SO₃H SO₃H H 1a²⁰⁹ SO₃H H H SO₃HNHCOCH₃ OMe CN H (2-Hydroxy H 1a²¹⁰ H SO₃H SO₃H H ethoxy)ethyl 1a²¹¹SO₃H H H SO₃H NHCOCH₃ OMe CN H 3-Isopropoxy propyl H 1a²¹² H SO₃H SO₃H H1a²¹³ SO₃H H H SO₃H NHCOCH₃ OMe CN H 3-Ethoxy propyl H 1a²¹⁴ H SO₃H SO₃HH 1a²¹⁵ SO₃H H H SO₃H NHCOCH₃ OMe CN H 4-Ethoxy butyl H 1a²¹⁶ H SO₃HSO₃H H 1a²¹⁷ SO₃H H H SO₃H NHCOCH₃ OMe CN H 3-(4-Hydroxybutoxy)- H 1a²¹⁸H SO₃H SO₃H H propyl 1a²¹⁹ SO₃H H H SO₃H Methyl Methyl CN H Ethyl Ethyl1a²²⁰ H SO₃H SO₃H H 1a²²¹ SO₃H H H SO₃H Methyl Methyl CN H Propyl Propyl1a²²² H SO₃H SO₃H H 1a²²³ SO₃H H H SO₃H Methyl Methyl CN H Butyl Butyl1a²²⁴ H SO₃H SO₃H H 1a²²⁵ SO₃H H H SO₃H Methyl Methyl CN H 2-Hydroxyethyl 2-Hydroxy ethyl 1a²²⁶ H SO₃H SO₃H H 1a²²⁷ SO₃H H H SO₃H MethylMethyl CN H Hexyl Hexyl 1a²²⁸ H SO₃H SO₃H H 1a²²⁹ SO₃H H H SO₃H MethylMethyl CN H Butyl Methyl 1a²³⁰ H SO₃H SO₃H H 1a²³¹ SO₃H H H SO₃H MethylMethyl CN H Butyl Ethyl 1a²³² H SO₃H SO₃H H 1a²³³ SO₃H H H SO₃H MethylMethyl CN H Cyclohexyl Methyl 1a²³⁴ H SO₃H SO₃H H 1a²³⁵ SO₃H H H SO₃HMethyl Methyl CN H Cyclohexyl Ethyl 1a²³⁶ H SO₃H SO₃H H 1a²³⁷ SO₃H H HSO₃H Methyl Methyl CN H Cyclohexyl 2-Hydroxyl ethyl 1a⁷³⁸ H SO₃H SO₃H H1a²³⁹ SO₃H H H SO₃H Methyl Methyl CONH₂ H Ethyl Ethyl 1a²⁴⁰ H SO₃H SO₃HH 1a²⁴¹ SO₃H H H SO₃H Methyl Methyl CONH₂ H Propyl Propyl 1a²⁴² H SO₃HSO₃H H 1a²⁴³ SO₃H H H SO₃H Methyl Methyl CONH₂ H Butyl Butyl 1a²⁴⁴ HSO₃H SO₃H H 1a²⁴⁵ SO₃H H H SO₃H Methyl Methyl CONH₂ H 2-Hydroxy ethyl2-Hydroxy ethyl 1a²⁴⁶ H SO₃H SO₃H H 1a²⁴⁷ SO₃H H H SO₃H Methyl MethylCONH₂ H Hexyl Hexyl 1a²⁴⁸ H SO₃H SO₃H H 1a²⁴⁹ SO₃H H H SO₃H MethylMethyl CONH₃ H Butyl Methyl 1a²⁵⁰ H SO₃H SO₃H H 1a²⁵¹ SO₃H H H SO₃HMethyl Methyl CONH₂ H Butyl Ethyl 1a²⁵² H SO₃H SO₃H H 1a²⁵³ SO₃H H HSO₃H Methyl Methyl CONH₂ H Cyclohexyl Methyl 1a²⁵⁴ H SO₃H SO₃H H 1a²⁵⁵SO₃H H H SO₃H Methyl Methyl CONH₂ H Cyclohexyl Ethyl 1a²⁵⁶ H SO₃H SO₃H H1a²⁵⁷ SO₃H H H SO₃H Methyl Methyl CONH₂ H Cyclohexyl 2-Hydroxyl ethyl1a²⁵⁸ H SO₃H SO₃H H 1a²⁵⁹ SO₃H H H SO₃H Methyl Methyl CONH₂ H 2-Hydroxyethyl H 1a²⁶⁰ H SO₃H SO₃H H 1a²⁶¹ SO₃H H H SO₃H NHCOCH₃ OMe CN H EthylEthyl 1a²⁶² H SO₃H SO₃H H 1a²⁶³ SO₃H H H SO₃H NHCOCH₃ OMe CN H PropylPropyl 1a²⁶⁴ H SO₃H SO₃H H 1a²⁶⁵ SO₃H H H SO₃H NHCOCH₃ OMe CN H ButylButyl 1a²⁶⁶ H SO₃H SO₃H H 1a²⁶⁷ SO₃H H H SO₃H NHCOCH₃ OMe CN H 2-Hydroxyethyl 2-Hydroxy ethyl 1a²⁶⁸ H SO₃H SO₃H H 1a²⁶⁹ SO₃H H H SO₃H NHCOCH₃OMe CN H Hexyl Hexyl 1a²⁷⁰ H SO₃H SO₃H H 1a²⁷¹ SO₃H H H SO₃H NHCOCH₃ OMeCN H Butyl Methyl 1a²⁷² H SO₃H SO₃H H 1a²⁷³ SO₃H H H SO₃H NHCOCH₃ OMe CNH Butyl Ethyl 1a²⁷⁴ H SO₃H SO₃H H 1a²⁷⁵ SO₃H H H SO₃H NHCOCH₃ OMe CN HCyclohexyl Methyl 1a²⁷⁶ H SO₃H SO₃H H 1a²⁷⁷ SO₃H H H SO₃H NHCOCH₃ OMe CNH Cyclohexyl Ethyl 1a²⁷⁸ H SO₃H SO₃H H 1a²⁷⁹ SO₃H H H SO₃H NHCOCH₃ OMeCN H Cyclohexyl 2-Hydroxyl ethyl 1a²⁸⁰ H SO₃H SO₃H H 1a²⁸¹ SO₃H H H SO₃HNHCOCH₃ OMe CONH₂ H Ethyl Ethyl 1a²⁸² H SO₃H SO₃H H 1a²⁸³ SO₃H H H SO₃HNHCOCH₃ OMe CONH₂ H Propyl Propyl 1a²⁸⁴ H SO₃H SO₃H H 1a²⁸⁵ SO₃H H HSO₃H NHCOCH₃ OMe CONH₂ H Butyl Butyl 1a²⁸⁶ H SO₃H SO₃H H 1a²⁸⁷ SO₃H H HSO₃H NHCOCH₃ OMe CONH₂ H 2-Hydroxy ethyl 2-Hydroxy ethyl 1a²⁸⁸ H SO₃HSO₃H H 1a²⁸⁹ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H Hexyl Hexyl 1a²⁹⁰ H SO₃HSO₃H H 1a²⁹¹ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H Butyl Methyl 1a²⁹² H SO₃HSO₃H H 1a²⁹³ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H Butyl Ethyl 1a²⁹⁴ H SO₃HSO₃H H 1a²⁹⁵ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H Cyclohexyl Methyl 1a²⁹⁶ HSO₃H SO₃H H 1a²⁹⁷ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H Cyclohexyl Ethyl1a²⁹⁸ H SO₃H SO₃H H 1a²⁹⁹ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H Cyclohexyl2-Hydroxyl ethyl 1a³⁰⁰ H SO₃H SO₃H H 1a³⁰¹ SO₃H H H SO₃H NHCOCH₃ OMeCONH₂ H 2-Hydroxy ethyl H 1a³⁰² H SO₃H SO₃H H 1a³⁰³ SO₃H H H SO₃HNHCOCH₃ OMe CONH₂ H 3-(4-Hydroxybutoxy)- H 1a³⁰⁴ H SO₃H SO₃H H propyl1a³⁰⁵ SO₃H H H SO₃H Methyl Methyl CN H 2-Chloro ethyl H 1a³⁰⁶ H SO₃HSO₃H H 1a³⁰⁷ SO₃H H H SO₃H Methyl Methyl CN H 2-(2-Hydroxy ethyl H 1a³⁰⁸H SO₃H SO₃H H sulfonyl)ethyl 1a³⁰⁹ SO₃H H H SO₃H Methyl Methyl CN H2-(2-tert Butyl sulfanyl H 1a³¹⁰ H SO₃H SO₃H H ethyl sulfonyl)ethyl1a³¹¹ SO₃H H H SO₃H Methyl Methyl CN H 2-(2-Hydroxy H 1a³¹² H SO₃H SO₃HH ethoxy)propyl 1a³¹³ SO₃H H H SO₃H Methyl Methyl CN H 3-(4-Hydroxy H1a³¹⁴ H SO₃H SO₃H H butoxy)propyl 1a³¹⁵ SO₃H H H SO₃H Methyl Methyl CN H3-(2-Phenoxy H 1a³¹⁶ H SO₃H SO₃H H ethoxyl)propyl 1a³¹⁷ SO₃H H H SO₃HMethyl Methyl CN H 3-Isopropxy propyl H 1a³¹⁸ H SO₃H SO₃H H 1a³¹⁹ SO₃H HH SO₃H Methyl Methyl CN H 3-Ethoxy propyl H 1a³²⁰ H SO₃H SO₃H H 1a³²¹SO₃H H H SO₃H Methyl Methyl CN H 4-Ethoxy butyl H 1a³²² H SO₃H SO₃H H1a³²³ SO₃H H H SO₃H Methyl Methyl CN H 4-(2-Hydroxy ethane H 1a³²⁴ HSO₃H SO₃H H sulfonyl)phenyl 1a³²⁵ SO₃H H H SO₃H Methyl Methyl CN H3-(2-Phenoxy H 1a³²⁶ H SO₃H SO₃H H ethoxyl)propyl 1a³²⁷ SO₃H H H SO₃HMethyl Methyl CONH₂ H 3-Chloro propyl H 1a³²⁸ H SO₃H SO₃H H 1a³²⁹ SO₃H HH SO₃H Methyl Methyl CONH₂ H 2-Methyl thioethyl H 1a³³⁰ H SO₃H SO₃H H1a³³¹ SO₃H H H SO₃H Methyl Methyl CONH₂ H 2-Fluoro ethyl H 1a³³² H SO₃HSO₃H H 1a³³³ SO₃H H H SO₃H Methyl Methyl CONH₂ H 2-(2-Hydroxy ethyl H1a³³⁴ H SO₃H SO₃H H sulfonyl)ethyl 1a³³⁵ SO₃H H H SO₃H Methyl MethylCONH₂ H 2-(2-tert Butyl sulfanyl H 1a³³⁶ H SO₃H SO₃H H ethylsulfonyl)ethyl 1a³³⁷ SO₃H H H SO₃H Methyl Methyl CONH₂ H 3-(2-Hydroxy H1a³³⁸ H SO₃H SO₃H H ethoxy)propyl 1a³³⁹ SO₃H H H SO₃H Methyl MethylCONH₂ H 2-(2-Hydroxy H 1a³⁴⁰ H SO₃H SO₃H H ethoxy)ethyl 1a³⁴¹ SO₃H H HSO₃H Methyl Methyl CONH₂ H 3-(4-Hydroxy H 1a³⁴² H SO₃H SO₃H Hbutoxy)propyl 1a³⁴³ SO₃H H H SO₃H Methyl Methyl CONH₂ H 3-(2-Phenoxy H1a³⁴⁴ H SO₃H SO₃H H ethoxyl)propyl 1a³⁴⁵ SO₃H H H SO₃H Methyl MethylCONH₂ H 3-Isopropxy propyl H 1a³⁴⁶ H SO₃H SO₃H H 1a³⁴⁷ SO₃H H H SO₃HMethyl Methyl CONH₂ H 3-Ethoxy propyl H 1a³⁴⁸ H SO₃H SO₃H H 1a³⁴⁹ SO₃H HH SO₃H Methyl Methyl CONH₂ H 4-Ethoxy butyl H 1a³⁵⁰ H SO₃H SO₃H H 1a³⁵¹SO₃H H H SO₃H Methyl Methyl CONH₂ H 4-(2-Hydroxy ethane H 1a³⁵² H SO₃HSO₃H H sulfonyl)phenyl 1a³⁵³ SO₃H H H SO₃H NHCOCH₃ OMe CN H 3-Chloropropyl H 1a³⁵⁴ H SO₃H SO₃H H 1a³⁵⁵ SO₃H H H SO₃H NHCOCH₃ OMe CN H2-Methyl thioethyl H 1a³⁵⁶ H SO₃H SO₃H H 1a³⁵⁷ SO₃H H H SO₃H NHCOCH₃ OMeCN H 2-Fluoroethyl H 1a³⁵⁸ H SO₃H SO₃H H 1a³⁵⁹ SO₃H H H SO₃H NHCOCH₃ OMeCN H 2-(2-Hydroxy ethyl H 1a³⁶⁰ H SO₃H SO₃H H sulfonyl)ethyl 1a³⁶¹ SO₃HH H SO₃H NHCOCH₃ OMe CN H 2-(2-tert Butyl sulfanyl H 1a³⁶² H SO₃H SO₃H Hethyl sulfonyl)ethyl 1a³⁶³ SO₃H H H SO₃H NHCOCH₃ OMe CN H 3-(2-Hydroxy H1a³⁶⁴ H SO₃H SO₃H H ethoxy)propyl 1a³⁶⁵ SO₃H H H SO₃H NHCOCH₃ OMe CN H2-(2-Hydroxy H 1a³⁶⁶ H SO₃H SO₃H H ethoxy)ethyl 1a³⁶⁷ SO₃H H H SO₃HMethyl Methyl CN H 3-(4-Hydroxy H 1a³⁶⁸ H SO₃H SO₃H H butoxy)propyl1a³⁶⁹ SO₃H H H SO₃H NHCOCH₃ OMe CN H 3-(2-Phenoxy H 1a³⁷⁰ H SO₃H SO₃H Hethoxyl)propyl 1a³⁷¹ SO₃H H H SO₃H NHCOCH₃ OMe CN H 3-Isopropxy propyl H1a³⁷² H SO₃H SO₃H H 1a³⁷³ SO₃H H H SO₃H NHCOCH₃ OMe CN H 3-Ethoxy propylH 1a³⁷⁴ H SO₃H SO₃H H 1a³⁷⁵ SO₃H H H SO₃H NHCOCH₃ OMe CN H 4-Ethoxybutyl H 1a³⁷⁶ H SO₃H SO₃H H 1a³⁷⁷ SO₃H H H SO₃H NHCOCH₃ OMe CN H4-(2-Hydroxy ethane H 1a³⁷⁸ H SO₃H SO₃H H sulfonyl)phenyl 1a³⁷⁹ SO₃H H HSO₃H NHCOCH₃ OMe CONH₂ H 2-Methyl thioethyl H 1a³⁸⁰ H SO₃H SO₃H H 1a³⁸¹SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H 2-Fluoroethyl H 1a³⁸² H SO₃H SO₃H H1a³⁸³ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H 2-Chloro ethyl H 1a³⁸⁴ H SO₃HSO₃H H 1a³⁸⁵ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H 2-(2-Hydroxy ethyl H1a³⁸⁶ H SO₃H SO₃H H sulfonyl)ethyl 1a³⁸⁷ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂H 2-(2-tert Butyl sulfanyl H 1a³⁸⁸ H SO₃H SO₃H H ethyl sulfonyl)ethyl1a³⁸⁹ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H 3-(2-Hydroxy H 1a³⁹⁰ H SO₃H SO₃HH ethoxy)propyl 1a³⁹¹ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H 2-(2-Hydroxy H1a³⁹² H SO₃H SO₃H H ethoxy)ethyl 1a³⁹³ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H3-(4-Hydroxy H 1a³⁹⁴ H SO₃H SO₃H H butoxy)propyl 1a³⁹⁵ SO₃H H H SO₃HNHCOCH₃ OMe CONH₂ H 3-(2-Phenoxy H 1a³⁹⁶ H SO₃H SO₃H H ethoxyl)propyl1a³⁹⁷ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H 3-Isopropxy propyl H 1a³⁹⁸ HSO₃H SO₃H H 1a³⁹⁹ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H 3-Ethoxy propyl H1a⁴⁰⁰ H SO₃H SO₃H H 1a⁴⁰¹ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H 4-Ethoxybutyl H 1a⁴⁰² H SO₃H SO₃H H 1a⁴⁰³ SO₃H H H SO₃H NHCOCH₃ OMe CONH₂ H4-(2-Hydroxy ethane H 1a⁴⁰⁴ H SO₃H SO₃H H sulfonyl)phenyl

Further particular preferred embodiments of the present invention arethe dyes of formula (1b) and mixtures thereof

wherein

R^(1b), R^(2b), R^(3b), R^(4b), R^(5b), R^(6b), R^(7b) and R^(8b)independent of each other is hydrogen, alkyl, alkoxy, halogen,trifluoromethyl or SO₃M, and wherein at least two of them are SO₃M,

R^(9b), R^(10b), R^(11b) and R^(12b) independent of each other ishydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen,trifluoromethyl(C₁-C₄)-acylamino or SO₃M,

R^(13b) and R^(18b) independent of each other is cyano, carbamoyl oralkoxycarbonyl,

R^(14b) and R^(19b) independent of each other is unsubstituted, linearor branched (C₁-C₄)-alkyl, unsubstituted (C₅-C₇)-cycloalkyl orsubstituted (C₅-C₇)-cycloalkyl with one or more substituents preferablyselected from the group consisting of methyl, ethyl, isobutyl,sec-butyl, tert-butyl and methylbutyl,

R^(15b), R^(16b), R^(20b) and R^(21b) independent of each other ishydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl,heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido,hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl,alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl,aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl,heteroarylalkyl, heterocycloalkylalkyl

or

alkyl interrupted by one or more heteroatoms selected from the groupconsisting of oxygen and sulphur

or

alkyl substituted by one or more substituents selected from the groupconsisting of hydroxy, aryl, cycloalkyl, alkoxy, amino,N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino,N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino,N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino,N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino,ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl,alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl,alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M

or

alkyl interrupted by one or more heteroatoms selected from the groupconsisting of oxygen and sulphur and substituted by one or moresubstituents selected from the group consisting of hydroxy, aryl,cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino,N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino,N-monocycloalkyl-amino, N,N-dicycloalkyl-amino,N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino,N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido,halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl,trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy,aryloyloxy, carbamoyl, sulfamoyl and SO₃M

or

joined together to form five or six membered ring being unsubstituted orsubstituted by one or more (C₁-C₄)-alkyl-groups and the ring beinguninterrupted or interrupted by one or more heteroatoms selected fromthe group consisting of oxygen and sulphur,

R^(17b) and R^(22b), independent from each other is hydrogen, (C₁-C₆)alkyl, (C₁-C₆) alkoxy, (C₁-C₆) alkyl terminated by halogen, hydroxyl

and

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaliearth metal or a monovalent organic cation.

In especially preferred dyes of formula (1b)

R^(1b), R^(3b), R^(4b), R^(5b), R^(6b) and R^(8b) independent of eachother is SO₃M, hydrogen, alkyl, alkoxy or halogen, whereby at least twoof them are SO₃M,

R^(2b) and R^(7b) is hydrogen,

R^(9b), R^(10b), R^(11b) and R^(12b) independent of each other ishydrogen, methyl, methoxy, ethoxy, halogen, —SO₃M or acetylamino,

R^(13b) and R^(18b) independent of each other is cyano or carbamoyl,

R^(14b) and R^(19b) is methyl,

R^(15b), R^(16b), R^(20b) and R^(21b) independent of each other ishydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl,3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl,1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl,2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl,2-methoxyethyl, 3-methoxypropyl, 2-cyanoethyl, 2-(methylthio)ethyl,2-fluoroethyl, 2-chloroethyl, 3-chloropropyl,2-(2-hydroxyethylsulfanyl)-ethyl,2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxy)propyl,2-(2-hydroxy ethoxy)ethyl, 3-(4-hydroxybutoxy)propyl,2-(2-hydroxyethanesulfonyl)-ethyl, 3-(2-phenoxy-ethoxy)-propyl,3-isopropoxy-propyl, 3-ethoxy-propyl, 3-ethoxybutyl

or

(C₂-C₆) alkyl substituted by COOM or by SO₃M

or

joined together to form five or six membered ring being unsubstituted orsubstituted by one or more (C₁-C₄)-alkyl-groups and the ring beinguninterrupted or interrupted by one or more heteroatoms selected fromthe group consisting of oxygen and sulphur,

R^(17b) and R^(22b) independent from each other is hydrogen or (C₁-C₆)alkyl

and

M is hydrogen, sodium, potassium, lithium or ammonium.

Examples of preferred dyes of formula (1b) are the compounds of formulae(1b¹ to 1b²⁴) and mixtures thereof, (Table 2) whereby R^(1b) and R^(8b)are hydrogen

R^(9b)/ R^(13b)/ R^(17b)/ R^(15b)/ R^(16b)/ S/No R^(3b) R^(4b) R^(5b)R^(6b) R^(10b)/R^(12b) R^(11b) R^(18b) R^(22b) R^(20b) R^(21b) 1b¹ 1b²SO₃H H H SO₃H H SO₃H SO₃H H Methyl Methyl CN H

1b³ 1b⁴ SO₃H H H SO₃H H SO₃H SO₃H H NHCOCH₃ OMe CN H

1b⁵ 1b⁶ SO₃H H H SO₃H H SO₃H SO₃H H Methyl Methyl CONH₂ H

1b⁷ 1b⁸ SO₃H H H SO₃H H SO₃H SO₃H H NHCOCH₃ OMe CONH₂ H

1b⁹ 1b¹⁰ SO₃H H H SO₃H H SO₃H SO₃H H Methyl Methyl CN H

1b¹¹ 1b¹² SO₃H H H SO₃H H SO₃H SO₃H H NHCOCH₃ OMe CN H

1b¹³ 1b¹⁴ SO₃H H H SO₃H H SO₃H SO₃H H Methyl Methyl CONH₂ H

1b¹⁵ 1b¹⁶ SO₃H H H SO₃H H SO₃H SO₃H H NHCOCH₃ OMe CONH₂ H

1b¹⁷ 1b¹⁸ SO₃H H H SO₃H H SO₃H SO₃H H Methyl Methyl CN H

1b¹⁹ 1b²⁰ SO₃H H H SO₃H H SO₃H SO₃H H NHCOCH₃ OMe CN H

1b²¹ 1b²² SO₃H H H SO₃H H SO₃H SO₃H H Methyl Methyl CONH₂ H

1b²³ 1b²⁴ SO₃H H H SO₃H H SO₃H SO₃H H NHCOCH₃ OMe CONH₂ H

* refers to the point of attachment to the nitrogen atom

Further preferred embodiments of the present invention are the dyes offormula (1c) and mixtures thereof

wherein

R^(1c), R^(2c), R^(3c), R^(4c), R^(5c), R^(6c), R^(7c) and R^(8c)independent of each other is hydrogen, alkyl, alkoxy, halogen,trifluoromethyl or SO₃M, whereby at least two of them are SO₃M,

R^(9c), R^(10c), R^(11c) and R^(12c) independent of each other ishydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, trifluoromethyl,(C₁-C₄)-acylamino or SO₃M,

R^(13c) and R^(18c) independent of each other is cyano, carbamoyl oralkoxycarbonyl,

R^(14c) and R^(19c) independent of each other is unsubstituted, linearor branched (C₁-C₄)-alkyl, unsubstituted (C₅-C₇)-cycloalkyl orsubstituted (C₅-C₇)-cycloalkyl with one or more substituents preferablyselected from the group consisting of methyl, ethyl, isobutyl,sec-butyl, tert-butyl and methylbutyl,

R^(15c), R^(16c), R^(17c), R^(20c), R^(21c) and R^(22c) independent ofeach other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl,cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido,phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl,amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl,aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl,aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl

or

alkyl interrupted by one or more heteroatoms selected from the groupconsisting of oxygen and sulphur

or

alkyl substituted by one or more substituents selected from the groupconsisting of hydroxy, aryl, cycloalkyl, alkoxy, amino,N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino,N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino,N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino,N,N-monoaryl-mono-cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino,ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl,alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl,alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M

or

alkyl interrupted by one or more heteroatoms selected from the groupconsisting of oxygen and sulphur and substituted by one or moresubstituents selected from the group consisting of hydroxy, aryl,cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino,N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino,N-monocycloalkyl-amino, N,N-dicycloalkyl-amino,N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino,N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido,halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl,trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy,aryloyloxy, carbamoyl, sulfamoyl and SO₃M

and

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaliearth metal or a monovalent organic cation.

In especially preferred dyes of formula (1c)

R^(1c), R^(3c), R^(4c), R^(5c), R^(6c) and R^(8c) independent of eachother is SO₃M, hydrogen, alkyl, alkoxy or halogen, whereby at least twoof them are SO₃M,

R^(2c) and R^(7c) is hydrogen,

R^(9c), R^(10c), R^(11c) and R^(12c) independent of each other ishydrogen, methyl, methoxy, ethoxy, halogen, —SO₃M or acetylamino,

R^(13c) and R^(18c) independent of each other is cyano or carbamoyl,

R^(14c) and R^(19c) is methyl,

R^(15c), R^(16c), R^(17c), R^(20c), R^(21c) and R^(22c) independent ofeach other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl,n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl,3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl,1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl,2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl,2-methoxyethyl, 3-methoxypropyl, 2-cyanoethyl, 2-(methylthio)ethyl,2-fluoroethyl, 2-chloroethyl, 3-chloropropyl,2-(2-hydroxyethylsulfanyl)-ethyl,2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxy)propyl,2-(2-hydroxy ethoxy)ethyl, 3-(4-hydroxybutoxy)propyl,2-(2-hydroxyethanesulfonyl)-ethyl, 3-(2-phenoxy-ethoxy)-propyl,3-isopropoxy-propyl, 3-ethoxy-propyl, 3-ethoxybutyl

or

(C₂-C₆) alkyl substituted by COOM or by SO₃M

and

M is hydrogen, sodium, potassium, lithium or ammonium.

Examples of preferred dyes of formula (1c) are the compounds of formulae(1c¹ to 1c¹⁸⁴) and mixtures thereof (Table 3):

Hereby R^(1c) and R^(8c) are hydrogen

TABLE 3 S/No R^(3c) R^(4c) R^(5c) R^(6c) R^(10c)/R^(12c) R^(9c)/R^(11c)R^(13c)/R^(18c) R^(17c)/R^(22c) R^(15c)/R^(20c) R^(16c)/R^(21c) 1c¹ SO₃HH H SO₃H 6-SO₃H H CN H Methyl H 1c² H SO₃H SO₃H H 1c³ SO₃H H H SO₃H6-SO₃H H CN H Ethyl H 1c⁴ H SO₃H SO₃H H 1c⁵ SO₃H H H SO₃H 6-SO₃H H CN HPropyl H 1c⁶ H SO₃H SO₃H H 1c⁷ SO₃H H H SO₃H 6-SO₃H H CN H Butyl H 1c⁸ HSO₃H SO₃H H 1c⁹ SO₃H H H SO₃H 6-SO₃H H CN H Pentyl H 1c¹⁰ H SO₃H SO₃H H1c¹¹ SO₃H H H SO₃H 6-SO₃H H CN H Hexyl H 1c¹² H SO₃H SO₃H H 1c¹³ SO₃H HH SO₃H 6-SO₃H H CN H Cyclobutyl H 1c¹⁴ H SO₃H SO₃H H 1c¹⁵ SO₃H H H SO₃H6-SO₃H H CN H Cyclopentyl H 1c¹⁶ H SO₃H SO₃H H 1c¹⁷ SO₃H H H SO₃H 6-SO₃HH CN H Cyclohexyl H 1c¹⁸ H SO₃H SO₃H H 1c¹⁹ SO₃H H H SO₃H 6-SO₃H H CN H2-Methyl H 1c²⁰ H SO₃H SO₃H H cyclohexyl 1c²¹ SO₃H H H SO₃H 6-SO₃H H CNH 3-Methyl H 1c²² H SO₃H SO₃H H cyclohexyl 1c²³ SO₃H H H SO₃H 6-SO₃H HCN H Isopropyl H 1c²⁴ H SO₃H SO₃H H 1c²⁵ SO₃H H H SO₃H 6-SO₃H H CN HSec-butyl H 1c²⁶ H SO₃H SO₃H H 1c²⁷ SO₃H H H SO₃H 6-SO₃H H CN H 2-MethylH 1c²⁸ H SO₃H SO₃H H butyl 1c²⁹ SO₃H H H SO₃H 6-SO₃H H CN H 1-Ethylpropyl H 1c³⁰ H SO₃H SO₃H H 1c³¹ SO₃H H H SO₃H 6-SO₃H H CN H1,2-Dimethyl H 1c³² H SO₃H SO₃H H propyl 1c³³ SO₃H H H SO₃H 6-SO₃H H CNH Tert-butyl H 1c³⁴ H SO₃H SO₃H H 1c³⁵ SO₃H H H SO₃H 6-SO₃H H CN H3-Methyl butyl H 1c³⁶ H SO₃H SO₃H H 1c³⁷ SO₃H H H SO₃H 6-SO₃H H CN HPentan-2-yl H 1c³⁸ H SO₃H SO₃H H 1c³⁹ SO₃H H H SO₃H 6-SO₃H H CN H2-Ethylhexyl H 1c⁴⁰ H SO₃H SO₃H H 1c⁴¹ SO₃H H H SO₃H 6-SO₃H H CN H2,2-Dimethyl H 1c⁴² H SO₃H SO₃H H propyl 1c⁴³ SO₃H H H SO₃H 6-SO₃H H CNH Phenyl H 1c⁴⁴ H SO₃H SO₃H H 1c⁴⁵ SO₃H H H SO₃H 6-SO₃H H CN H Benzyl H1c⁴⁶ H SO₃H SO₃H H 1c⁴⁷ SO₃H H H SO₃H 7-SO₃H H CN H Methyl H 1c⁴⁸ H SO₃HSO₃H H 1c⁴⁹ SO₃H H H SO₃H 7-SO₃H H CN H Ethyl H 1c⁵⁰ H SO₃H SO₃H H 1c⁵¹SO₃H H H SO₃H 7-SO₃H H CN H Propyl H 1c⁵² H SO₃H SO₃H H 1c⁵³ SO₃H H HSO₃H 7-SO₃H H CN H Butyl H 1c⁵⁴ H SO₃H SO₃H H 1c⁵⁵ SO₃H H H SO₃H 7-SO₃HH CN H Pentyl H 1c⁵⁶ H SO₃H SO₃H H 1c⁵⁷ SO₃H H H SO₃H 7-SO₃H H CN HHexyl H 1c⁵⁸ H SO₃H SO₃H H 1c⁵⁹ SO₃H H H SO₃H 7-SO₃H H CN H Cyclobutyl H1c⁶⁰ H SO₃H SO₃H H 1c⁶¹ SO₃H H H SO₃H 7-SO₃H H CN H Cyclopentyl H 1c⁶² HSO₃H SO₃H H 1c⁶³ SO₃H H H SO₃H 7-SO₃H H CN H Cyclohexyl H 1c⁶⁴ H SO₃HSO₃H H 1c⁶⁵ SO₃H H H SO₃H 7-SO₃H H CN H 2-Methyl H 1c⁶⁶ H SO₃H SO₃H Hcyclohexyl 1c⁶⁷ SO₃H H H SO₃H 7-SO₃H H CN H 3-Methyl H 1c⁶⁸ H SO₃H SO₃HH cyclohexyl 1c⁶⁹ SO₃H H H SO₃H 7-SO₃H H CN H Isopropyl H 1c⁷⁰ H SO₃HSO₃H H 1c⁷¹ SO₃H H H SO₃H 7-SO₃H H CN H Sec-butyl H 1c⁷² H SO₃H SO₃H H1c⁷³ SO₃H H H SO₃H 7-SO₃H H CN H 2-Methyl H 1c⁷⁴ H SO₃H SO₃H H butyl1c⁷⁵ SO₃H H H SO₃H 7-SO₃H H CN H 1-Ethyl propyl H 1c⁷⁶ H SO₃H SO₃H H1c⁷⁷ SO₃H H H SO₃H 7-SO₃H H CN H 1,2-Dimethyl H 1c⁷⁸ H SO₃H SO₃H Hpropyl 1c⁷⁹ SO₃H H H SO₃H 7-SO₃H H CN H Tert-butyl H 1c⁸⁰ H SO₃H SO₃H H1c⁸¹ SO₃H H H SO₃H 7-SO₃H H CN H 3-Methyl butyl H 1c⁸² H SO₃H SO₃H H1c⁸³ SO₃H H H SO₃H 7-SO₃H H CN H Pentan-2-yl H 1c⁸⁴ H SO₃H SO₃H H 1c⁸⁵SO₃H H H SO₃H 7-SO₃H H CN H 2-Ethylhexyl H 1c⁸⁶ H SO₃H SO₃H H 1c⁸⁷ SO₃HH H SO₃H 7-SO₃H H CN H 2,2-Dimethyl H 1c⁸⁸ H SO₃H SO₃H H propyl 1c⁸⁹SO₃H H H SO₃H 7-SO₃H H CN H Phenyl H 1c⁹⁰ H SO₃H SO₃H H 1c⁹¹ SO₃H H HSO₃H 7-SO₃H H CN H Benzyl H 1c⁹² H SO₃H SO₃H H 1c⁹³ SO₃H H H SO₃H 6-SO₃HH CONH₂ H Methyl H 1c⁹⁴ H SO₃H SO₃H H 1c⁹⁵ SO₃H H H SO₃H 6-SO₃H H CONH₂H Ethyl H 1c⁹⁶ H SO₃H SO₃H H 1c⁹⁷ SO₃H H H SO₃H 6-SO₃H H CONH₂ H PropylH 1c⁹⁸ H SO₃H SO₃H H 1c⁹⁹ SO₃H H H SO₃H 6-SO₃H H CONH₂ H Butyl H 1C¹⁰⁰ HSO₃H SO₃H H 1c¹⁰¹ SO₃H H H SO₃H 6-SO₃H H CONH₂ H Pentyl H 1c¹⁰² H SO₃HSO₃H H 1c¹⁰³ SO₃H H H SO₃H 6-SO₃H H CONH₂ H Hexyl H 1c¹⁰⁴ H SO₃H SO₃H H1c¹⁰⁵ SO₃H H H SO₃H 6-SO₃H H CONH₂ H Cyclobutyl H 1c¹⁰⁶ H SO₃H SO₃H H1c¹⁰⁷ SO₃H H H SO₃H 6-SO₃H H CONH₂ H Cyclopentyl H 1c¹⁰⁸ H SO₃H SO₃H H1c¹⁰⁹ SO₃H H H SO₃H 6-SO₃H H CONH₂ H Cyclohexyl H 1c¹¹⁰ H SO₃H SO₃H H1c¹¹¹ SO₃H H H SO₃H 6-SO₃H H CONH₂ H 2-Methyl H 1c¹¹² H SO₃H SO₃H Hcyclohexyl 1c¹¹³ SO₃H H H SO₃H 6-SO₃H H CONH₂ H 3-Methyl H 1c¹¹⁴ H SO₃HSO₃H H cyclohexyl 1c¹¹⁵ SO₃H H H SO₃H 6-SO₃H H CONH₂ H Isopropyl H 1c¹¹⁶H SO₃H SO₃H H 1c¹¹⁷ SO₃H H H SO₃H 6-SO₃H H CONH₂ H Sec-butyl H 1c¹¹⁸ HSO₃H SO₃H H 1c¹¹⁹ SO₃H H H SO₃H 6-SO₃H H CONH₂ H 2-Methyl H 1c¹²⁰ H SO₃HSO₃H H butyl 1c¹²¹ SO₃H H H SO₃H 6-SO₃H H CONH₂ H 1-Ethyl propyl H 1c¹²²H SO₃H SO₃H H 1c¹²³ SO₃H H H SO₃H 6-SO₃H H CONH₂ H 1,2-Dimethyl H 1c¹²⁴H SO₃H SO₃H H propyl 1c¹²⁵ SO₃H H H SO₃H 6-SO₃H H CONH₂ H Tert-butyl H1c¹²⁶ H SO₃H SO₃H H 1c¹²⁷ SO₃H H H SO₃H 6-SO₃H H CONH₂ H 3-Methyl butylH 1c¹²⁸ H SO₃H SO₃H H 1c¹²⁹ SO₃H H H SO₃H 6-SO₃H H CONH₂ H Pentan-2-yl H1c¹³⁰ H SO₃H SO₃H H 1c¹³¹ SO₃H H H SO₃H 6-SO₃H H CONH₂ H 2-Ethylhexyl H1c¹³² H SO₃H SO₃H H 1c¹³³ SO₃H H H SO₃H 6-SO₃H H CONH₂ H 2,2-Dimethyl H1c¹³⁴ H SO₃H SO₃H H propyl 1c¹³⁵ SO₃H H H SO₃H 6-SO₃H H CONH₂ H Phenyl H1c¹³⁶ H SO₃H SO₃H H 1c¹³⁷ SO₃H H H SO₃H 6-SO₃H H CONH₂ H Benzyl H 1c¹³⁸H SO₃H SO₃H H 1c¹³⁹ SO₃H H H SO₃H 7-SO₃H H CONH₂ H Methyl H 1c¹⁴⁰ H SO₃HSO₃H H 1c¹⁴¹ SO₃H H H SO₃H 7-SO₃H H CONH₂ H Ethyl H 1c¹⁴² H SO₃H SO₃H H1c¹⁴³ SO₃H H H SO₃H 7-SO₃H H CONH₂ H Propyl H 1c¹⁴⁴ H SO₃H SO₃H H 1c¹⁴⁵SO₃H H H SO₃H 7-SO₃H H CONH₂ H Butyl H 1c¹⁴⁶ H SO₃H SO₃H H 1c¹⁴⁷ SO₃H HH SO₃H 7-SO₃H H CONH₂ H Pentyl H 1c¹⁴⁸ H SO₃H SO₃H H 1c¹⁴⁹ SO₃H H H SO₃H7-SO₃H H CONH₂ H Hexyl H 1c¹⁵⁰ H SO₃H SO₃H H 1c¹⁵¹ SO₃H H H SO₃H 7-SO₃HH CONH₂ H Cyclobutyl H 1c¹⁵² H SO₃H SO₃H H 1c¹⁵³ SO₃H H H SO₃H 7-SO₃H HCONH₂ H Cyclopentyl H 1c¹⁵⁴ H SO₃H SO₃H H 1c¹⁵⁵ SO₃H H H SO₃H 7-SO₃H HCONH₂ H Cyclohexyl H 1c¹⁵⁶ H SO₃H SO₃H H 1c¹⁵⁷ SO₃H H H SO₃H 7-SO₃H HCONH₂ H 2-Methyl H 1c¹⁵⁸ H SO₃H SO₃H H cyclohexyl 1c¹⁵⁹ SO₃H H H SO₃H7-SO₃H H CONH₂ H 3-Methyl H 1c¹⁶⁰ H SO₃H SO₃H H cyclohexyl 1c¹⁶¹ SO₃H HH SO₃H 7-SO₃H H CONH₂ H Isopropyl H 1c¹⁶² H SO₃H SO₃H H 1c¹⁶³ SO₃H H HSO₃H 7-SO₃H H CONH₂ H Sec-butyl H 1c¹⁶⁴ H SO₃H SO₃H H 1c¹⁶⁵ SO₃H H HSO₃H 7-SO₃H H CONH₂ H 2-Methyl butyl H 1c¹⁶⁶ H SO₃H SO₃H H 1c¹⁶⁷ SO₃H HH SO₃H 7-SO₃H H CONH₂ H 1-Ethyl propyl H 1c¹⁶⁸ H SO₃H SO₃H H 1c¹⁶⁹ SO₃HH H SO₃H 7-SO₃H H CONH₂ H 1,2-Dimethyl H 1c¹⁷⁰ H SO₃H SO₃H H propyl1c¹⁷¹ SO₃H H H SO₃H 7-SO₃H H CONH₂ H Tert-butyl H 1c¹⁷² H SO₃H SO₃H H1c¹⁷³ SO₃H H H SO₃H 7-SO₃H H CONH₂ H 3-Methyl butyl H 1c¹⁷⁴ H SO₃H SO₃HH 1c¹⁷⁵ SO₃H H H SO₃H 7-SO₃H H CONH₂ H Pentan-2-yl H 1c¹⁷⁶ H SO₃H SO₃H H1c¹⁷⁷ SO₃H H H SO₃H 7-SO₃H H CONH₂ H 2-Ethylhexyl H 1c¹⁷⁸ H SO₃H SO₃H H1c¹⁷⁹ SO₃H H H SO₃H 7-SO₃H H CONH₂ H 2,2-Dimethyl H 1c¹⁸⁰ H SO₃H SO₃H Hpropyl 1c¹⁸¹ SO₃H H H SO₃H 7-SO₃H H CONH₂ H Phenyl H 1c¹⁸² H SO₃H SO₃H H1c¹⁸³ SO₃H H H SO₃H 7-SO₃H H CONH₂ H Benzyl H 1c¹⁸⁴ H SO₃H SO₃H H

The present invention also provides a process for the preparation of thedyes of formula (1) and mixtures thereof, comprising the steps

a) diazotization of a compound of formula (2)

wherein R¹ to R⁸ are defined as given above,

b) reacting diazonium salt obtained in step a) with the compounds offormula (3) and (4) in stoichiometric amounts

wherein R⁹ to R¹² are defined as given above, to yield an intermediateof formula (5)

c) diazotization of the compound of formula (5),

d) reacting the diazonium salts obtained in step c) with the compoundsof the formula (6), (7), (8) and (9) or mixtures thereof

wherein R¹³ to R²² are defined as given above.

The diazotization of the compound of formula (2) and (5), respectivelycan be performed by means of diazotization methods that are known to aperson skilled in the art, preferably by using sodium nitrite ornitrosylsulfuric acid in acidic medium using inorganic acids such ashydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereofor organic acids such as acetic acid or propionic acid or mixturesthereof. Also mixtures of inorganic acid with organic acids can beadvantageously used.

The coupling reaction of the diazonium salts obtained by diazotizationof the compound of the formula (2) onto the compounds of formulae (3)and (4) as well as the coupling reaction of the diazonium salts obtainedby diazotization of the compound of the formula (5) onto the compoundsof formulae (6), (7), (8) and (9) can likewise be performed by knownmethods.

The compounds of formula (2) are known and commercially available andcan also be synthesised by means of common chemical reactions known to aperson skilled in the art such as the methods disclosed in U.S. Pat. No.5,728,874 or DE172106.

The pyridines of formula (6), (7), (8) and (9) in which R¹³ and R¹⁸denote cyano are commercially available or can be synthesized viamethods disclosed in the literature such as DE2230392. Through analogy,all the pyridine derivatives that are used in this invention can besynthesized with the protocol. The obtained pyridines can be furtherderivatized by reactions known to persons skilled in the art, such ashydrolysis to form pyridines of formula (6), (7), (8) and (9) in whichR¹³ and R¹⁸ are carbonamide or by hydrolysis and further esterificationto form pyridine derivatives in which R¹³ and R¹⁸ are alkoxycarbonyl.

The above-mentioned derivatization reactions can be carried out inalkaline or acidic media, preferably in acidic media using stronginorganic acids such as sulfuric acid or hydrochloric acid gaseous orsolution, acidic resins or chlorotrimethylsilane or other suitable acidcatalyst in the presence of the corresponding alcohol. The reactions areadvantageously carried out under inert atmosphere at temperatures in therange from 40 to 150° C.

Alternatively, the above mentioned derivatization reactions can beundertaken as a final step after the synthesis of the corresponding dyeswith pyridine nitriles.

The dyes of the present invention can be used alone or as a mixture withother dyes according to the present invention and/or other substances.

Thus a chemical composition comprising one or more dye(s) as describedabove is also an aspect of the present invention.

A chemical composition consisting of two or more dyes as described aboveforms another preferred aspect of the present invention.

Also an aqueous solution for dyeing comprising one or more dye(s) asdescribed above forms an aspect of the present invention.

The dyes of the present invention are suitable for dyeing and printingof natural, manufactured, regenerated, modified or synthetic hydroxyl-amino-, and/or carboxamido-containing fiber materials and their blendsby the application methods numerously described in the art for aciddyes.

Therefore, the present invention also provides a process for dyeing andprinting of the above-mentioned fiber materials and their blends inwhich a dye or a dye mixture according to the present invention is used.

The use of a dye as described above, a chemical composition as describedabove or of an aqueous solution as described above for dyeing fibers, aswell as blends of such fibres selected from the group consisting of:synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 andaramid fibres, vegetable fibres, seed fibres, cotton, organic cotton,kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf,ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres,bamboo; fibres from animals, wool, organic wool, silk, cashmere wool,alpaca fiber, mohair, Angora fibre as well as fur and leather materials;manufactured, regenerated and recycled fibres, cellulosic fibres; paperfibres, cellulosic regenerated fibres, viscose rayon fibres, acetate andtriacetate fibers and Lyocell fibers forms another aspect of the presentinvention.

Still another aspect of the present invention is/are: Fiber and blendscontaining such fiber selected from the group consisting of: syntheticfiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres,vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir fromcoconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaffibres, sisal, henequen, banana; stalk fibres, bamboo; fibres fromanimals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair,Angora fibre as well as fur and leather materials; manufactured,regenerated and recycled fibres, cellulosic fibres; paper fibres,cellulosic regenerated fibres, viscose rayon fibres, acetate andtriacetate fibers, and Lyocell fibers comprising one or more dye(s) ofthe present invention either in chemically and/or physically bound form.

The above-mentioned substrates to be dyed can be present in variousforms such as but not limited to yarn, woven fabric, loop-forminglyknitted fabric or carpet. For instance in the form of sheetlikestructures, such as paper and leather, in the form of films, such asnylon films, or in the form of a bulk mass, for example composed ofpolyamide and polyurethane, in particular in the form of fibers, forexample cellulose fibers. The fibers are preferably textile fibers, forexample in the form of woven fabrics or yarns or in the form of hanks orwound packages,

The dyes of the present invention and their salts and/or mixtures can beused as a single dyeing colorant in dyeing or printing processes or canbe part of a di-, tri- or multi-component combination colorant in dyeingor in printing compositions. The di-, tri- or multi-component shadedyeings show similar fastness level as compared to dyeing performed witha single colorant component.

Dyes of the present invention and their salts or mixtures are highlycompatible with other known and/or commercially available acid dyes andthey can be used together with such dyes of related chromophores andsimilar technical performance to obtain specific hues. Similar technicalperformance includes: comparable build-up, comparable fastnessproperties and comparable exhaustion rates during dyeings.

The dyes according to the invention can be applied to the materialsmentioned, especially the fiber materials mentioned, by the applicationtechniques known for water-soluble dyes. This applies to both, dyeingand printing processes.

It applies in particular to the production of dyeings on fiber materialscomposed of wool or other natural polyamides or of synthetic polyamidesand their mixtures with other fiber material. In general, the materialto be dyed is introduced into the bath at a temperature of about 40° C.,agitated therein for some time, the dyebath is then adjusted to thedesired weakly acidic, preferably weakly acetic acid, pH and the actualdyeing is carried out at a temperature between 60 and 98° C. However,the dyeings can also be carried out at the boil or in a sealed dyeingapparatus at temperatures of up to 106° C.

Since the water solubility of the dyes according to the invention isvery good, they can also be used with advantage in customary continuousdyeing processes.

The dyes of the present invention can also be used in digital printingprocesses, in particular in digital textile printing. For this the dyesof the present invention need to be formulated in aqueous inks.

An Ink for digital textile printing, comprising a dye of the presentinvention is another aspect of the present invention.

The inks of the present invention comprise the dye of the presentinvention in amounts which preferably range from 0.1 to 50% by weight,more preferably from 0.5 to 30% by weight and most preferably from 1 to15% by weight, based on the total weight of the ink.

If desired the inks may contain further dyes used in digital printing inaddition to the one or more dyes of the present invention.

For the inks of the present invention to be used in the continuous flowprocess, a conductivity of 0.5 to 25 mS/m can be set by adding anelectrolyte. Useful electrolytes include for example lithium nitrate andpotassium nitrate. The inks of the present invention may include organicsolvents at a total level of 1 to 50% by weight and preferably 5 to 30%by weight. Suitable organic solvents are for example alcohols, forexample methanol, ethanol, 1-propanol, isopropanol, 1-butanol,tert-butanol, pentyl alcohol, polyhydric alcohols for example:1,2-ethanediol, 1,2,3-propanetriol, butanediol, 1,3-butanediol,1,4-butanediol, 1,2-propanediol, 2,3-propanediol, pentanediol,1,4-pentanediol, 1,5-pentanediol, hexanediol, D,L-1,2-hexanediol,1,6-hexanediol, 1,2,6-hexanetriol, 1,2-octanediol, polyalkylene glycols,for example: polyethylene glycol, polypropylene glycol, alkylene glycolshaving 1 to 8 alkylene groups, for example: monoethylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol,thiodiglycol, butyltriglycol, hexylene glycol, propylene glycol,dipropylene glycol, tripropylene glycol, low alkyl ethers of polyhydricalcohols, for example: ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, ethylene glycol monobutyl ether, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, diethylene glycolmonobutyl ether, diethylene glycol monohexyl ether, triethylene glycolmonomethyl ether, triethylene glycol monobutyl ether, tripropyleneglycol monomethyl ether, tetraethylene glycol monomethyl ether,tetraethylene glycol monobutyl ether, tetraethylene glycol dimethylether, propylene glycol monomethyl ether, propylene glycol monoethylether, propylene glycol monobutyl ether, tripropylene glycol isopropylether, polyalkylene glycol ethers, such as for example: polyethyleneglycol monomethyl ether, polypropylene glycol glycerol ether,polyethylene glycol tridecyl ether, polyethylene glycol nonylphenylether, amines, such as for example: methylamine, ethylamine,triethylamine, diethylamine, dimethylamine, trimethylamine,dibutylamine, diethanolamine, triethanolamine, N-acetylethanolamine,N-formylethanolamine, ethylenediamine, urea derivatives, such as forexample: urea, thiourea, N-methylurea, N,N′-epsilon dimethylurea,ethyleneurea, 1,1,3,3-tetramethylurea, amides, such as for example:dimethylformamide, dimethylacetamide, acetamide, ketones or ketoalcohols, such as for example: acetone, diacetone alcohol, cyclicethers, such as for example: tetrahydrofuran, trimethylolethane,trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol,gamma butyrolactone, epsilon-caprolactam, further sulfolane,dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethylsulfone, butadiene sulfone, dimethyl sulfoxide, dibutyl sulfoxide,N-cyclohexylpyrrolidone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone,2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone,1-(3-hydroxypropyl)-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone,1,3-dimethyl-2-imidazolinone, 1,3-bismethoxymethylimidazolidine,2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol,2-(2-butoxyethoxy)ethanol, 2-(2-propoxyethoxy)ethanol, pyridine,piperidine, butyrolactone, trimethylpropane, 1,2-dimethoxypropane,dioxane ethyl acetate, ethylenediaminetetraacetate ethyl pentyl ether,1,2-dimethoxypropane and trimethylpropane.

The inks of the present invention may further include customaryadditives, for example viscosity moderators to set viscosities in therange from 1.5 to 40.0 mPas in a temperature range from 20 to 50° C.Preferred inks have a viscosity of 1.5 to 20 mPas and particularlypreferred inks have a viscosity of 1.5 to 15 mPas.

Useful viscosity moderators include rheological additives, for example:polyvinylcaprolactam, polyvinylpyrrolidone and their copolymerspolyetherpolyol, associative thickeners, polyurea, polyurethane, sodiumalginates, modified galactomannans, polyetherurea, polyurethane,nonionic cellulose ethers.

As further additives the inks of the invention may includesurface-active substances to set surface tensions of 20 to 65 mN/m,which are adapted if necessary as a function of the process used(thermal or piezo technology). Useful surface-active substances includefor example: all surfactants, preferably nonionic surfactants,butyldiglycol, 1,2-hexanediol.

The inks of the present invention may further comprise customaryadditives, for example substances to inhibit fungal and bacterial growthin amounts from 0.01 to 1% by weight based on the total weight of theink.

The inks may be prepared in a conventional manner by mixing thecomponents in water.

The inks of the invention are particularly useful in inkjet printingprocesses for printing a wide variety of pretreated materials, such assilk, leather, wool, polyamide fibers and polyurethanes, and cellulosicfiber materials of any kind. Blend fabrics, for example blends ofcotton, silk, wool with polyester fibers or polyamide fibers cansimilarly be printed.

In contrast to conventional textile printing, where the printing inkalready contains all necessary chemicals, in digital or inkjet printingthe auxiliaries have to be applied to the textile substrate in aseparate pretreatment step.

The pretreatment of the textile substrate, for example cellulose andregenerated cellulose fibers and also silk and wool, is effected with anaqueous alkaline liquor prior to printing. In addition there is a needfor thickeners to prevent flowing of the motives when the printing inkis applied, for example sodium alginates, modified polyacrylates orhighly etherified galactomannans.

These pretreatment reagents are uniformly applied to the textilesubstrate in a defined amount using suitable applicators, for exampleusing a 2- or 3-roll pad, contactless spraying technologies, by means offoam application or using appropriately adapted inkjet technologies, andsubsequently dried.

The examples below serve to illustrate the invention. Parts andpercentages are by weigh unless noted otherwise. The relationshipbetween parts by weight and parts by volume is that of the kilogram tothe liter.

EXAMPLE 1

8.62 g of 4,4′-Diamino-biphenyl-2,2′-disulfonic acid was first dissolvedin water at slightly acidic pH to give a complete solution. Ice wasadded to the solution and when temperature reached 10 to 15° C., 10.6 mlof 5 N sodium nitrite solution were added dropwise. The reaction mixturewas further cooled down to 0 to 8° C. when the mixture was addeddropwise into 12.38 g of concentrated HCl with 12 g of ice. Yellowsuspension was formed and reaction mixture was completed within an hour.

6.30 g of 2,5-Dimethyl-phenylamine were added directly into the diazosuspension and stirred. A violet precipitate was observed upon addition.The obtained intermediate precipitate,4,4′-Bis-(4-amino-2,5-dimethyl-phenylazo)-biphenyl-2,2′-disulfonic acid,was filtered off with suction and washed with organic solvent and dried.

15.22 g of the dried intermediate,4,4′-Bis-(4-amino-2,5-dimethyl-phenylazo)-biphenyl-2,2e-disulfonic acid,was then dissolved in water at slightly acidic pH to give a completereddish orange solution. Ice was added to the solution and when thetemperature reached 10 to 15° C., 10.1 ml of 5 N sodium nitrite solutionwere added dropwise. The reaction mixture was further cooled down to 0to 8° C. when the mixture was added dropwise into concentrated HCl withice. Violet suspension was formed and reaction mixture was completed in90 mins.

The obtained reaction mixture was used in the next step as describedbelow: 11.63 g of6-Hydroxy-2-(3-methoxy-propylamino)-4-methyl-nicotinonitrile werestirred in methanol and adjusted to slightly acidic. The reactionmixture was added dropwise into the methanol solution and stirred.Brilliant orange precipitate was observed upon addition. Precipitateobtained was filtered off with suction and washed with brine givingproduct of the formula 1a¹⁹⁰. The analytic data are consistent with theassigned structure for product 1a¹⁹⁰. The product dyes the targetedfibre materials in brilliant scarlet to red shades.

Through analogy, all the dyes of formulae (1a¹-1a⁴⁰⁴)(1b¹-1b²⁴) and(1c¹-1c¹⁸⁴) can be synthesized according to the method described above.

DYEING EXAMPLE 1

1 part of the dye 1a¹⁹⁰ of this invention was dissolved in 2000 parts ofwater and 1 part of levelling assistant (based on condensation productof a higher aliphatic amine and ethylene oxide) and 6 parts of sodiumacetate were added. The pH was then adjusted to 5 using acetic acid(80%). The dyebath was heated to 50° C. for 10 minutes and then enteredwith 100 parts of a woven polyamide-6 fabric. The temperature was raisedto 98° C. over the course of 50 minutes and then dyeing was carried outat this temperature for 60 minutes. This was followed by cooling to 60°C. and removal of the dyed material. The polyamide-6 fabric was washedwith hot and cold water, soaped and then spun and dried. The dyeingobtained gave red shade and has very good light and wet fastness andalso good levelness in the fibre.

DYEING EXAMPLE 2

1 part of the dye 1a¹⁹⁰ of this invention was dissolved in 2000 parts ofwater and 1 part of levelling assistant (based on condensation productof a higher aliphatic amine and ethylene oxide) and 6 parts of sodiumacetate were added. The pH was then adjusted to 5.5 using acetic acid(80%). The dyebath was heated to 50° C. for 10 minutes and then enteredwith 100 parts of a woven polyamide-6,6 fabric. The temperature wasraised to 120° C. over the course of 50 minutes and then dyeing wascarried out at this temperature for 60 minutes. This was followed bycooling to 60° C. and removal of the dyed material. The polyamide-6,6fabric was washed with hot and cold water, soaped and then spun anddried. The dyeing obtained gave red shade and has very good light andwet fastness and also good levelness in the fibre.

DYEING EXAMPLE 3

100 parts of polyamide-6 material were padded with a 1000 parts 50° C.liquor solution that consisted of 40 parts of the dye 1a¹⁹⁰, 100 partsof urea, 20 parts of a non ionic solubilizer based on butyldiglycol, 20parts of acetic acid to adjust the pH to 4.0, 10 parts of levellingassistant (based on ethoxylated aminopropyl fatty acid amide) and 815parts of water. The material was rolled up and placed into a steamingchamber at 85 to 98° C. for 3 to 6 hours. After fixation, the fabric waswashed with hot and cold water, soaped and then spun and dried. Thedyeing obtained gave red shade and has very good light and wet fastnessand also good levelness in the fibre.

DYEING EXAMPLE 4

1 part of the dye 1a¹⁹⁰ of this invention was dissolved in 2000 parts ofwater and 5 parts of sodium sulphate, and 1 part of levelling assistant(based on condensation product of a higher aliphatic amine and ethyleneoxide) and 5 parts of sodium acetate are added. The pH was then adjustedto 4.5 using acetic acid (80%). The dyebath was heated to 50° C. for 10minutes and then entered with 100 parts of a woven wool fabric. Thetemperature was raised to 100° C. over the course of 50 minutes and thendyeing was carried out at this temperature for 60 minutes. This wasfollowed by cooling to 90° C. and removal of the dyed material. The woolfabric was washed with hot and cold water, soaped and then spun anddried. The dyeing obtained gave red shade and has very good light andwet fastness and also good levelness in the fibre.

DYEING EXAMPLE 5

1 part of the dye 1a¹⁹⁰ of this invention was dissolved in 1000 parts ofsoft water and 7.5 parts of sodium sulphate and 1 part of a wettingagent (anionic) were added. 100 parts of bleached cotton knitted fabricwere added to this solution. The dye bath was then heated up to 98° C.with a gradient of 2° C./min, then dyeing was carried out at thistemperature for 60 minutes. This was followed by cooling down to 80° C.At 80° C. the dyeing was continued for another 20 minutes. The dyedmaterial was then removed and was washed with hot and cold water, soapedand then spun and dried. The dyeings obtained gave red shade and hasvery good light and wet fastness and also good levelness in the fibre.

EXAMPLE 6 Preparation of an Ink

3 parts of the dye 1a¹⁹⁰ of this invention dissolved in 82 parts ofdeionized water was added into the dyebath with 15 parts of diethyleneglycol at 60° C. On cooling, a red printing ink was obtained. The redprinting ink can be used for ink jet printing on paper, polyamide orwool textiles.

DYEING EXAMPLE 7

4 parts of chemically bleached (pine wood) sulphite pulp was mixed upwith 100 parts of 55° C. water. 1 part of the dye 1a¹⁹⁰ of thisinvention was dissolved in 100 parts of hot water. 80 parts of thissolution were given to the mixed-up pulp and mixed for 2 minutes. Afterthat the mixture was sized with resin size in a conventional manner andmixed for another 2 minutes. 55 parts of this solution were then dilutedwith 2000 parts of cold water and the paper was produced out of thissolution. The red paper produced from the mixture has good wetfastnesses.

The invention claimed is:
 1. A dye of formula (1)

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independent of each other ishydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO₃M, whereby atleast two of them are SO₃M, R⁹, R¹⁰, R¹¹, R¹² independent of each otheris hydrogen, alkyl, substituted alkyl, alkyl chain interrupted by one ortwo heteroatoms selected from the group consisting of oxygen and sulphuralkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl,heterocycloalkyl, cyano, acyloxy, alkylcarbonyl, acylamino,alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino,dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl,alkoxycarbonyl, carbamoyl, sulfamoyl, ureido, —SO₃M or alkylureido, R¹³and R¹⁸ independent of each other is cyano, carbamoyl, substitutedcarbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl orhalogen, R¹⁴ and R¹⁹ independent of each other is hydrogen, alkyl,cycloalkyl, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl,COOM, amino, hydroxyl, monocycloalkyl-amino, monoalkyl-amino,di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl-amino,monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio orarylthio, or is alkyl substituted by one or more substituents selectedfrom the group consisting of hydroxy, cycloalkyl, heteroaryl,heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen,cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino,acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino,ureido, alkylureido and phenylureido, R¹⁵, R¹⁶, R¹⁷, R²⁰, R²¹ and R²²independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy,alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl,alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl,amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl,aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl,aryloxyalkyl, arylthioxyalkyl, or heteroarylalkyl,heterocycloalkylalkyl, or alkyl interrupted by one or more heteroatomsselected from the group consisting of oxygen and sulphur, or alkylsubstituted by one or more substituents selected from the groupconsisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino,N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino,N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino,N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino,N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino,ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl,thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl,heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy,aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl,N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl,N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl,N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl,sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl,N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl,N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl,N-monoalkyl-N-monoarylsulfamoyl and SO₃M, or alkyl interrupted by one ormore heteroatoms selected from the group consisting of oxygen andsulphur and substituted by one or more substituents selected from thegroup consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy,amino, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino,N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino,N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino,N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino,ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl,thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl,heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy,aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl,N-monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl,N,N-dialkyl-carbamoyl, N-monoaryl-carbamoyl, N,N-diaryl-carbamoyl,N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl,sulfamoyl, N-monocycloalkyl-sulfamoyl, N-monoalkyl-sulfamoyl,N,N-dicycloalkyl-sulfamoyl, N,N-dialkyl-sulfamoyl, N-monoaryl-sulfamoyl,N,N-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl,N-monoalkyl-N-monoarylsulfamoyl and SO₃M, M is hydrogen, an alkalimetal, ammonium, one equivalent of an alkali earth metal or a monovalentorganic cation, the dyes of formula (1) have two to six sulfonic acidgroups, and whereby the bonds with unfixed attachment points on thepyridine couplers mean that the amino rests bearing the substituents R¹⁵and R¹⁶, and —OR¹⁷, respectively can be positioned ortho or para to R¹³,meaning that when the amino rest bearing the substituents R¹⁵ and R¹⁶ ispositioned ortho to R¹³, the —OR¹⁷ is positioned para to R¹³, and viceversa; and the same applies to the amino rests bearing the substituentsR²⁰ and R²¹, and —OR²², respectively that can be positioned ortho orpara to R¹⁸, meaning that when the amino rest bearing, the substituentsR²⁰ and R²¹ is positioned ortho to R¹⁸, the —OR²² is positioned para toR¹⁸, and vice versa.
 2. The dye according to claim 1, having formula(1a)

wherein R^(1a), R^(2a), R^(3a), R^(4a), R^(5a), R^(6a), R^(7a) andR^(8a) independent of each other is hydrogen, alkyl, alkoxy, halogen,trifluoromethyl or SO₃M, whereby at least two of them are SO₃M, R^(9a),R^(10a), R^(11a) and R^(12a) independent of each other is hydrogen,(C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, trifluoromethyl, —SO₃M or(C₁-C₄)-acylamino, R^(13a) and R^(18a) independent of each other iscyano, carbamoyl or alkoxycarbonyl, R^(14a) and R^(19a) independent ofeach other is unsubstituted, linear or branched (C₁-C₄)-alkyl,unsubstituted (C₅-C₇)-cycloalkyl or substituted (C₅-C₇)-cycloalkyl withone or more substituents, R^(15a), R^(16a) R^(17a), R^(20a), R^(21a) andR^(22a) independent of each other is hydrogen, alkyl, hydroxyalkyl,alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl,carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonyl-alkyl,aminoalkyl, amino-hydroxyalkyl, alkoxyalkylaminoalkyl,thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl,cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl orheterocycloalkylalkyl, or alkyl interrupted by one or more heteroatomsselected from the group consisting of oxygen and sulphur, or alkylsubstituted by one or more substituents selected from the groupconsisting of hydroxy, aryl, cycloalkyl, alkoxy, amino,N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino,N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino,N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino,N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino,ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl,alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl,alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M, oralkyl interrupted by one or more heteroatoms selected from the groupconsisting of oxygen and sulphur and substituted by one or moresubstituents selected from the group consisting of hydroxy, aryl,cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino,N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino,N-monocycloalkyl-amino, N,N-dicycloalkyl-amino,N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino,N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido,halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl,trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy,aryloyloxy, carbamoyl, sulfamoyl and SO₃M, and M is hydrogen, an alkalimetal, ammonium, one equivalent of an alkali earth metal or a monovalentorganic cation.
 3. The dye according to claim 2, wherein R^(1a), R^(3a),R^(4a), R^(5a), R^(6a) and R^(8a) independent of each other is SO₃M,hydrogen, alkyl, alkoxy or halogen, whereby at least two of them areSO₃M, R^(2a) and R^(7a) is hydrogen, R^(9a), R^(10a), R^(11a) andR^(12a) independent of each other is hydrogen, methyl, methoxy, ethoxy,halogen, —SO₃M or acetylamino, R^(13a) and R^(18a) independent of eachother is cyano or carbamoyl, R^(14a) and R^(19a) is methyl, R^(15a),R^(16a), R^(20a) and R^(21a) independent of each other is hydrogen,methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl,cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl,isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl,tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl,2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl,2-methoxyethyl, 3-methoxypropyl, 2-cyanoethyl, 2-(methylthio)ethyl,2-fluoroethyl, 2-chloroethyl, 3-chloropropyl,2-(2-hydroxyethylsulfanyl)-ethyl,2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxy)propyl,2-(2-hydroxy ethoxy)ethyl, 3-(4-hydroxybutoxy)propyl,2-(2-hydroxyethanesulfonyl)-ethyl, 3-(2-phenoxy-ethoxy)-propyl,3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, R^(17a) andR^(22a) independent of each other is hydrogen, (C₁-C₆) alkyl or (C₁-C₆)alkyl interrupted by —O— or —S—, and M is hydrogen, sodium, potassium,lithium or ammonium.
 4. The dye according to claim 1, having formula(1b)

wherein R^(1b), R^(2b), R^(3b), R^(4b), R^(5b), R^(6b), R^(7b) andR^(8b) independent of each other is hydrogen, alkyl, alkoxy, halogen,trifluoromethyl or SO₃M, whereby at least two of them are SO₃M, R^(9b),R^(10b), R^(11b) and R^(12b) independent of each other is hydrogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, trifluoromethyl,(C₁-C₄)-acylamino or SO₃M, R^(13b) and R^(18b) independent of each otheris cyano, carbamoyl or alkoxycarbonyl, R^(14b) and R^(19b) independentof each other is unsubstituted, linear or branched (C₁-C₄)-alkyl,unsubstituted (C₅-C₇)-cycloalkyl or substituted (C₅-C₇)-cycloalkyl withone or more substituents, R^(15b), R^(16b), R^(20b) and R^(21b)independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy,alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl,alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl,amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl,aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl,aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl or heterocycloalkylalkyl,or alkyl interrupted by one or more heteroatoms selected from the groupconsisting of oxygen and sulphur, or alkyl substituted by one or moresubstituents selected from the group consisting of hydroxy, aryl,cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino,N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino,N-monocycloalkyl-amino, N,N-dicycloalkyl-amino,N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino,N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido,halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl,trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy,aryloyloxy, carbamoyl, sulfamoyl and SO₃M, or alkyl interrupted by oneor more heteroatoms selected from the group consisting of oxygen andsulphur and substituted by one or more substituents selected from thegroup consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino,N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino,N,N-diaryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino,N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino,N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido,halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl,trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy,aryloyloxy, carbamoyl, sulfamoyl and SO₃M, or joined together to formfive or six membered ring being unsubstituted or substituted by one ormore (C₁-C₄)-alkyl-groups and the ring being uninterrupted orinterrupted by one or more heteroatoms selected from the groupconsisting of oxygen and sulphur, R^(17b) and R^(22b) independent fromeach other is hydrogen, (C₁-C₆) alkyl, (C₁-C₆) alkoxy, (C₁-C₆) alkylterminated by halogen or hydroxyl, and M is hydrogen, an alkali metal,ammonium, one equivalent of an alkali earth metal or a monovalentorganic cation.
 5. The dye according to claim 4, wherein R^(1b), R^(3b),R^(4b), R^(5b), R^(6b) and R^(8b) independent of each other is SO₃M,hydrogen, alkyl, alkoxy or halogen, whereby at least two of them areSO₃M, R^(2b) and R^(7b) is hydrogen, R^(9b), R^(10b), R^(11b) andR^(12b) independent of each other is hydrogen, methyl, methoxy, ethoxy,halogen or acetylamino, R^(13b) and R^(18b) independent of each other iscyano or carbamoyl, R^(14b) and R^(19b) is methyl, R^(15b), R^(16b),R^(20b) and R^(21b) independent of each other is hydrogen, methyl,ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl,cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl,sec-butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl,3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl,benzyl, 2-hydroxyethyl, allyl, 2-methoxyethyl, 3-methoxypropyl,2-cyanoethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl,3-chloropropyl, 2-(2-hydroxyethylsulfanyl)-ethyl,2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxy)propyl,2-(2-hydroxy ethoxy)ethyl, 3-(4-hydroxybutoxy)propyl,2-(2-hydroxyethanesulfonyl)-ethyl, 3-(2-phenoxy-ethoxy)-propyl,3-isopropoxy-propyl, 3-ethoxy-propyl, 3-ethoxybutyl or (C₂-C₆) alkylsubstituted by COOM or SO₃M, or joined together to form five or sixmembered ring being unsubstituted or substituted by one or more(C₁-C₄)-alkyl-groups and the ring being uninterrupted or interrupted byone or more heteroatoms selected from the group consisting of oxygen andsulphur, R^(17b) and ^(R22b) independent from each other is hydrogen or(C₁-C₆) alkyl and M is hydrogen, sodium, potassium, lithium or ammonium.6. The dye according to claim 1, having formula (1c)

wherein R^(1c), R^(2c), R^(3c), R^(4c), R^(5c), R^(6c), R^(7c) andR^(8c) independent of each other is hydrogen, alkyl, alkoxy, halogen,trifluoromethyl or SO₃M, wherein at least two of them are SO₃M, R^(9c),R^(10c), R^(11c) and R^(12c) independent of each other is hydrogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, halogen, trifluoromethyl,(C₁-C₄)-acylamino or SO₃M, R^(13c) and R^(18c) independent of each otheris cyano, carbamoyl or alkoxycarbonyl, R^(14c) and R^(19c) independentof each other is unsubstituted, linear or branched (C₁-C₄)-alkyl,unsubstituted (C₅-C₇)-cycloalkyl or substituted (C₅-C₇)-cycloalkyl withone or more substituents, R^(15c), R^(16c), R^(17c), R^(20c), R^(21c)and R^(22c) independent of each other is hydrogen, alkyl, hydroxyalkyl,alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl,carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl,aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl,thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl,cycloalkyl alkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl orheterocycloalkylalkyl, or alkyl interrupted by one or more heteroatoms,selected from the group consisting of oxygen and sulphur, or alkylsubstituted by one or more substituents selected from the groupconsisting of hydroxy, aryl, cycloalkyl, alkoxy, amino,N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino,N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino,N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino,N,N-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino,ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl,alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl,alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO₃M, oralkyl interrupted by one or more heteroatoms selected from the groupconsisting of oxygen and sulphur and substituted by one or moresubstituents selected from the group consisting of hydroxy, aryl,cycloalkyl, alkoxy, amino, N-monoalkyl-amino, N,N-dialkyl-amino,N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino,N-monocycloalkyl-amino, N,N-dicycloalkyl-amino,N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino,N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido,halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl,trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy,aryloyloxy, carbamoyl, sulfamoyl and SO₃M, and M is hydrogen, an alkalimetal, ammonium, one equivalent of an alkali earth metal or a monovalentorganic cation.
 7. The dye according to claim 6, wherein R^(1c), R^(3c),R^(4c), R^(5c), R^(6c) and R^(8c) independent of each other is SO₃M,hydrogen, alkyl, alkoxy or halogen, wherein at least two of them areSO₃M, R^(2c) and R^(7c) is hydrogen, R^(9c), R^(10c), R^(11c) andR^(12c) independent of each other is hydrogen, methyl, methoxy, ethoxy,halogen, —SO₃M or acetylamino, R^(13c) and R^(18c) independent of eachother is cyano or carbamoyl, R^(14c) and R^(19c) is methyl, R^(15c),R^(16c), R^(17c), R^(20c), R^(21c) and R^(22c) independent of each otheris hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl,3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1-ethylpropyl,1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl,2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl,2-methoxyethyl, 3-methoxypropyl, 2-cyanoethyl, 2-(methylthio)ethyl,2-fluoroethyl, 2-chloroethyl, 3-chloropropyl,2-(2-hydroxyethylsulfanyl)-ethyl,2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2-hydroxyethoxy)propyl,2-(2-hydroxy ethoxy)ethyl, 3-(4-hydroxybutoxy)propyl,2-(2-hydroxyethanesulfonyl)-ethyl, 3-(2-phenoxy-ethoxy)-propyl,3-isopropoxy-propyl, 3-ethoxy-propyl or 3-ethoxybutyl, or (C₂-C₆) alkylsubstituted by COOM or SO₃M, and M is hydrogen, sodium, potassium,lithium or ammonium.
 8. A process for the production of the dyeaccording to claim 1, comprising the steps a) diazotization of acompound of formula (2)

wherein R¹ to R⁸ are defined as in claim 1, b) reacting diazonium saltobtained in step a) with the compounds of formula (3) and (4) instoichiometric amounts

wherein R⁹ to R¹² are defined as in claim 1, to yield an intermediate offormula (5)

c) diazotization of the compound of formula (5), d) reacting thediazonium salts obtained in step c) with the compounds of the formula(6), (7), (8) and (9) or mixtures thereof

wherein R¹¹ to R²⁴ are defined as in claim
 1. 9. A chemical compositioncomprising one or more dye(s) according to claim
 1. 10. A chemicalcomposition consisting essentially of two or more dyes according toclaim
 1. 11. An aqueous solution for dyeing comprising one or morechemical compounds according to claim
 9. 12. A process for dyeing orprinting carboxamido- and/or hydroxyl-containing material, comprisingcontacting the carboxamido- and/or hydroxyl-containing material with thedye according to claim
 1. 13. An ink for digital textile printing,comprising the dye according to claim
 1. 14. A process for dying fiberswhich comprises contacting the fiber with the dye according to claim 1,wherein the fiber is selected from the group consisting of: syntheticfiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres,vegetable fibers, seed fibers, cotton, organic cotton, kapok, coir fromcoconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaffibers, sisal, henequen, banana; stalk fibers, bamboo; fibers fromanimals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair,Angora fiber, fur, leather materials; manufactured, regenerated andrecycled fibers, cellulosic fibers; paper fibers, cellulosic regeneratedfibers, viscose rayon fibers, acetate and triacetate fibers and Lyocellfibers.
 15. A fiber and blends containing a fiber selected from thegroup consisting on synthetic fiber materials, nylon materials, nylon-6,nylon-6.6 and aramid fibres, vegetable fibers, seed fibers, cotton,organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp,jute, kenaf, ramie, rattan; leaf fibers, sisal, henequen, banana; stalkfibers, bamboo; fibers from animals, wool, organic wool, silk, cashmerewool, alpaca fiber, mohair, Angora fiber, fur, leather materials;manufactured, regenerated and recycled fibers, cellulosic fibers; paperfibers, cellulosic regenerated fibers, viscose rayon fibers, acetate andtriacetate fibers, and Lyocell fibers comprising one or more dye(s)according to claim 1 either in chemically and/or physically bound formon the fiber.